Substituted 1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonyl chlorides

ABSTRACT

Novel substituted triazolo[1,5-a]pyrimidine-2-sulfonamides, e.g., 5,7-dimethyl-N-(2,6-dichlorophenyl)-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonamide and their agriculturally acceptable salt are prepared. These compounds and compositions containing them are useful for the control of unwanted vegetation. Novel substituted triazolo[1,5-a]pyrimidine-2-sulfonyl chlorides and substituted anilines and their use as intermediates are also described.

CROSS-REFERENCE TO RELATED APPLICATION

This application is a divisional application of application Ser. No.940,480, filed Dec. 10, 1986, now U.S. Pat. No. 4,818,273, which is acontinuation-in-part of application Ser. No. 768,393, filed Aug. 22,1985, now abandoned, which is a continuation in part of application Ser.No. 551,758, filed Nov. 14, 1983 now abandoned. The disclosure of thespecification and claims of application Ser. No. 768,393 is herebyincorporated by reference.

BACKGROUND OF THE INVENTION

In recent years there has been a great deal of effort directed to thedevelopment of sulfonamides having herbicidal activity and several ofthese compounds have reached the stage of commercialization, i.e.,chlorosulfuron and sulfometuron methyl. These compounds exhibit bothpreemergence and postemergence activity against undesirable vegetationand, in addition, have a low toxicity to mammals. The compounds of theprior art may be depicted as follows: ##STR1## wherein Ar is usually abenzene derivative and Ar' is usually a pyrimidine or symmetricaltriazine derivative.

In addition, there are a number of other sulfonamide herbicides thathave been commercialized, for example, methyl sulfanilylcarbamate;O,O-diisopropyl phosphorodithioate-S-ester withN-(2-mercaptoethyl)benzenesulfonamide;3-isopropyl-1H-2,1,3-benzothiadiazin-4(3H)-one-2,2-dioxide;N-[2,4-dimethyl-5-[[(trifluoromethyl)sulfonyl]amino]phenyl]acetamide and3,5-dinitro-N⁴, N⁴ -dipropylsulfanilamide.

It has now been found that novel compounds having the formula: ##STR2##wherein

Ar represets an aromatic or heteroaromatic ring chosen from amongphenyl; 1- or 2-naphthyl; 2-, 3- or 4-pyridyl; 2-or 3-thienyl; 2- or3-furyl; 2-, 4-, or 5-thiazolyl; 2-, 4-, or 5-imidazolyl; 2-, 4-, or5-oxazolyl; 3-, 4-, or 5-isothiazolyl; 3-, 4-, or 5-isoxazolyl; 3-, 4-,or 5-pyrazolyl; 2-benzthiazolyl; 2-benzoxazolyl; 2-benzimidazolyl: or1-benztriazolyl; and Ar is unsubstituted except in the case of where Aris phenyl or Ar is substituted with one to five substituents chosen fromamong C₁ -C₆ alkyl; benzyl; halo; C₁ -C₆ mono- or polyhaloalkyl; phenyl;phenyl substituted with one or more groups chosen from halo, C₁ -C₆alkyl, or C₁ -C₆ haloalkyl; hydroxy; C₁ -C₆ alkoxy; C₁ -C₆ mono- orpolyhaloalkoxy; phenoxy; phenoxy substituted with one or more groupschosen from halo, C₁ -C₆ alkyl or C₁ -C₆ haloalkyl; 2-pyridyloxy;2-pyridyloxy substituted with one or more groups, chosen from halo, C₁-C₆ alkyl or C₁ -C₆ haloalkyl; amino; C₁ -C₆ alkylamino; C₁ -C₆dialkylamino; nitro; C₁ -C₆ alkylthio; C₁ -C₆ polyhaloalkylthio; C₁ -C₆alkylsulfinyl; C₁ -C₆ polyhaloalkylsulfinyl; C₁ -C₆ alkylsulfonyl; C₁-C₆ polyhaloalkylsulfonyl; phenylthio; phenylthio substituted with oneor more groups chosen from halo, C₁ -C₆ alkyl or C₁ -C₆ haloalkyl;phenylsulfinyl; phenylsulfinyl substituted with one or more groupschosen from halo, C₁ -C₆ alkyl, or C₁ -C₆ haloalkyl; phenylsulfonyl;phenylsulfonyl substituted with one or more groups chosen from halo, C₁-C₆ alkyl, or C₁ -C₆ haloalkyl; cyano; carboxyl; C₁ -C₁₀ alkoxycarbonyl;phenoxycarbonyl; phenoxycarbonyl substituted withone or more groupschosen from halo, C₁ -C₆ alkyl or C₁ -C₆ haloalkyl; alkoxyalkoxycarbonylwherein the number of carbons in the alkoxyalkoxy fragment ranges from2-10 and the number of oxygens in the alkoxyalkoxy fragment ranges from2-4; 2-pyridylmethoxycarbonyl; dialkylaminoalkoxycarbonyl wherein thenumber of carbons in the dialkylaminoalkoxy fragment ranges from 3-10and the number of oxygens in the dialkylaminoalkoxy fragment is one; C₃-C₆ alkenyloxycarbonyl; COON═C(R¹⁴)(R¹⁴) wherein each R¹⁴ independentlyrepresents hydrogen, C₁ -C₆ alkyl or phenyl; amino-, C₁ -C₆ alkylamino-,or di C₁ -C₆ alkylaminocarbonyl; C₁ -C₁₀ alkoxysulfonyl; C₁ -C₄polyhaloalkoxysulfonyl; di C₁ -C₆ alkylaminosulfonyl; formyl; C₁ -C₆alkylcarbonyl; C₁ -C₆ mono- or polyhaloalkylcarbonyl; phenylcarbonyl;phenylcarbonyl substituted with one or more groups chosen from halo, C₁-C₆ alkyl or C₁ -C₆ haloalkyl; or C(R¹⁵)(R¹⁵)OR¹⁶ wherein each R¹⁵independently represents hydrogen or C₁ -C₆ alkyl and R¹⁶ representshydrogen, C₁ -C₆ alkyl, benzyl, phenylcarbonyl or C₁ -C₆ alkylcarbonyl(except in the cases of thio, sulfinyl, and sulfonyl substituents whereif one of these substituents is present the other one to four Arsubstituents may not be chosen from among the other two; oxycarbonylsubstituents where the other one to four Ar substituents may not bechosen from among different oxycarbonyl substituents; or aminocarbonylsubstituents where the other one to four Ar substituents may not bechosen from among different aminocarbonyl substituents); X, Y, and Zindependently represent hydroxyl; carboxyl; hydrogen; C₁ -C₆ alkyl; C₁-C₆ mono- or polyhaloalkyl; C₁ -C₆ alkoxy; C₁ -C₆ mono- orpolyhaloalkoxy; amino, C₁ -C₄ alkylamino, or di C₁ -C₄ alkylamino;phenyl; phenyl substituted with one or more groups chosen from halo,nitro, C₁ -C₆ alkyl, or C₁ -C₆ mono- or polyhaloalkyl; C₁ -C₆ alkylthio;halo; or two adjacent substituents (i.e., X and Y or Y and Z) are joinedtogether to form a five, six, or seven-membered saturated cyclicstructure of carbon atoms or one said carbon atom of X,Y or Y,Z isreplaced by a heteroatom chosen from among nitrogen, oxygen, or sulfur(i.e., X,Y or Y,Z is --(CH₂)_(n) -- wherein n is 3, 4, or 5; or X,Y orY,Z is --(CH₂)_(n) --A--(CH₂)_(m) -- wherein n is 0-4, the value of m isequal to the ring size minus (n+3) and A is NH, O, or S); and V is H orR and R represents C₁ -C₁₀ alkyl, C₃ -C₁₀ alkenyl, C₃ -C₁₀ alkynyl,phenylalkyl, C₂ -C₁₀ alkanoyl, C₁ -C₁₀ alkoxycarbonyl, phenoxycarbonyl,di C₁ -C₆ alkylaminocarbonyl, C₁ -C₆ alkylsulfonyl, phenylsulfonyl, C₁-C₁₀ alkoxythiocarbonyl or phenoxythiocarbonyl, wherein alkyl, alkenyl,alkynyl, and alkoxy in each instance is optionally substituted by haloand each phenyl moiety is optionally substituted by one or two groupsselected from halo, nitro, C₁ -C₄ alkyl, or C₁ -C₄ haloalkyl; and, whenV represents hydrogen, agriculturally acceptable salts thereof areuseful pre- and post-emergence herbicides or intermediates for preparingherbicides.

Treatment of the locus of undesired vegetation or weeds with the novelcompounds or with compositions containing herbicidally effective amountsof the novel compounds in admixture with one or more inert carriers canbe used to obtain broad spectrum or selective weed control dependingupon the specific compound and the amount applied. Broadleaf weeds areparticularly susceptible to the compounds and control of undesirablevegetation in crops such as wheat, rice, corn, soybeans, and cotton canbe achieved. Aquatic vegetation is controlled by the compounds.

In addition, certain novel tetrahydro derivatives of the compounds ofgeneral Formula I, which can be represented by Formula II ##STR3##wherein X, Y, A, V, and Ar as defined hereinabove and theiragriculturally acceptable salts also exhibit herbicidal activity.

The invention further encompasses certain of the novel substitutedtriazolo[1,5-a]pyrimidine-2-sulfonyl chlorides and certain of the novelsubstituted anilines which are useful in preparing the compounds ofFormulae I and II.

DETAILED DESCRIPTION OF THE INVENTION

The contemplated aromatic or heteroaromatic ring systems, Ar, of FormulaI include substituted or unsubstituted (except for phenyl, which must besubstituted) phenyl; 1- or 2-naphthyl; 2-, 3- or 4-pyridyl; 2- or3-thienyl; 2-or 3-furyl; 2-, 4- or 5-thiazolyl; 2-, 4- or 5-imidazolyl;2-, 4- or 5-oxazolyl; 3-, 4- or 5-isothiazolyl; 3-, 4- or 5-isoxazolyl;3-, 4- or 5-pyrazolyl; 2-benzthiazolyl; 2-benzoxazolyl; 2-benzimidazolyland 1-benztriazolyl. Typical examples of substituents found on thearomatic or heteroaromatic ring systems may be one, more than one, or acombination of the following: halo, C₁ -C₆ alkyl, benzyl, C₁ -C₆ mono-or polyhaloalkyl, phenyl (optionally substituted with one or more groupschosen from halo, C₁ -C₆ alkyl, or C₁ -C₆ haloalkyl), hydroxy, C₁-C.sub. 6 alkoxy, C₁ -C₆ mono- or polyhaloalkoxy, phenoxy or yridyloxy(each optionally substituted with one or more groups chosen from halo,C₁ -C₆ alkyl or C₁ -C₆ haloalkyl), nitro, amino, C₁ -C₆ alkylamino, diC₁ -C₆ alkylamino, C₁ -C₆ alkylthio, C₁ -C₆ polyhaloalkylthio, C₁ -C₆alkylsulfinyl, C₁ -C₆ polyhaloalkylsulfinyl, C₁ -C₆ alkylsulfonyl, C₁-C₆ polyhaloalkylsulfonyl, phenylthio or phenylsulfinyl orphenylsulfonyl (each phenyl optionally substituted wit one or moregroups chosen from halo, C₁ -C₆ alkyl, or C₁ -C₆ haloalkyl), cyano,carboxylic acids and derivatives of carboxylic acids (esters derivedfrom available alcohols and amides derived from ammonia or availableprimary and secondary amines, which can be termed oxycarbonyl andaminocarbonyl substituents) including C₁ -C₁₀ alkoxycarbonyl,pheoxycarbonyl optionally substituted with one or more groups chosenfrom halo, C₁ -C₆ alkyl, or C₁ -C₆ haloalkyl, alkoxyalkoxycarbonylwherein the number of carbons in the alkoxyalkoxy fragment ranges from2-10 and the number of oxygens in the alkoxyalkoxy fragment ranges from2-4, 2-pyridylmethoxycarbonyl, dialkylaminoalkoxycarbonyl wherein thenumber of carbons in the dialkylaminoalkoxy fragment ranges from 3-10and the number of oxygens in the dialkylaminoalkoxy fragment is one, C₃-C₆ alkenyloxycarbonyl, COON═C(R¹⁴)(R¹⁴) wherein each R¹⁴ independentlyrepresents hydrogen, C₁ -C₆ alkyl, or phenyl, C₁ -C₁₀ alkoxysulfonyl, C₁-C₄ polyhaloalkoxysulfonyl, amino- or C₁ -C₆ alkylamino or di C₁ -C.sub.6 alkylaminocarbonyl, di C₁ -C₆ alkylaminosulfonyl, formyl, C₁ -C₆alkylcarbonyl; C₁ -C₆ mono- or polyhaloalkylcarbonyl, phenylcarbonyl(optionally substituted with one or more groups selected from halo, C₁-C₆ alkyl, or C₁ -C₆ haloalkyl), or C(R¹⁵)( R¹⁵)OR¹⁶ wherein each R¹⁵independently represents hydrogen or C₁ -C₆ alkyl and R¹⁶ representshydrogen, C₁ -C₆ alkyl, benzyl, phenylcarbonyl, or C₁ -C₆ alkylcarbonyl.In cases where one substituent is a thio, sulfinyl, or sulfonyl moiety,other substituents may not be chosen from among the other two. Also, incases where one substituent is an oxycarbonyl moiety, other substituentsmay not be chosen from among other oxycarbonyl moieties; and where onesubstituent is an aminocarbonyl moiety, other substituents may not bechosen from among other aminocarbonyl moieties. Halo in each instancerepresents fluoro, chloro, bromo, or iodo.

Compounds of Formula I wherein Ar represents substituted phenyl orsubstituted or unsubstituted 1- or 2-naphthyl; 2-, 3-, or 4-pyridyl; 2-or 3-thienyl; or 3-, 4-, or 5-pyrazolyl are preferred. Those wherein Arrepresents substituted phenyl, substituted 1-naphthyl, or substituted3-, 4-, or 5-pyrazolyl are more preferred.

In the case of the more preferred compounds of Formula I wherein Ar issubstituted phenyl, Ar can be depicted as the formula ##STR4## whereinR¹, R², R³, R⁴, and R⁵ independently represent each of the Arsubstituents (with each of the listed exceptions) noted in the Summaryof the Invention and in the foregoing discussion, or hydrogen, providednot all are hydrogen. Of those substituents, the following arepreferred. R¹ represents F, Cl, Br, I, --NO₂, phenyl, phenoxy(optionallysubstituted by one or more substituents selected from F, Cl,Br, I, C₁ -C₄ alkyl, and C₁ -C₄ haloalkyl), --CF₃, --OCF₃, OCF₂ CF₂ H,--OCF₂ CCl₂ H, --OCH₂ CF₃, --SCF₃, --SCF₂ CF₂ H, --SCF₂ CCl₂ H, --SOCF₃,--SOCF₂ CF₂ H, --SOCF₂ CCl₂ H, --SO₂ CF₃, --SO₂ CF₂ CF₂ H, --SO₂ CF₂CCl₂ H, --SR⁶, --SOR⁶, --SO₂ R⁶, --CN, --COOR⁷, --CONH.sub. 2, --CONHR⁸,--CONR⁸ R⁸, --SO₃ R⁸, or SO₃ CH₂ CF₃ ; R² and R⁴ represent H, F, Cl, Br,I, C₁ -C₄ alkyl, --COOR⁷, or --OR⁸ ; R³ is H; and R⁵ represents H,phenyl, C₁ -C₄ alkyl, C₁ -C₄ alkoxy, F, Cl, Br, I, --NO₂, --CF₃,--OCF₃,--OCF₂ CF₂ H, --OCF₂ CCl₂ H, --OCH₂ CF₃, --SCF₃, --SCF₂ CF₂ H, --SCF₂CCl₂ H, --SOCF₃, --SOCF₂ CF₂ H, --SOCF₂ CCl₂ H, --SO₂ CF₃, --SO₂ CF₂ CF₂H, --SO₂ CF₂ CCl₂ H, --SR⁶, --SOR⁶, --SO₂ R⁶, --CN, --COOR⁷, --CONH₂,--CONHR⁸, --CONR⁸ R⁸, --SO₃ R⁸, --SO₃ CH₂ CF₃, or --CR⁶ R⁶ OR⁶, whereinR⁶ represents H or C₁ -C₄ alkyl, R⁷ represents C₁ -C₆ alkyl, C₃ 14 C₄alkenyl, C₃ -C₄ alkynyl, C₁ -C₄ alkoxy C₂ -C₃ alkyl, phenyl (optionallysubstituted by one or two substituents selected from F, Cl, Br, I, C₁-C₄ alkyl, and C₁ -C₄ haloalkyl), or 2-pyridylmethyl and R⁸ representsC₁ -C₄ alkyl.

Compounds of Formula I in which Ar is represented by the formula##STR5## wherein R¹ represents C₁ -C₄ alkyll, F, Cl, Br I, --NO₂, --SR⁶,--SOR⁶, --SO₂ R⁶, --COOR⁷, or --CF₃ ; R² represents H, F, Cl, Br, I, C₁-C₄ alkyl, or --COOR⁷ and R⁵ represents H, C₁ -C₄ alkyl, C₁ -C₄ alkoxy,F, Cl, Br, I, --CH₂ OR⁶, phenyl, --NO₂, or --COOR⁷ wherein R⁶ representsC₁ -C₄ alkyl and R⁷ represents C₁ -C₄ alkyl, C₃ -C₄ alkenyl, C₃ -C₄alkynyl, 2-ethoxyethyl or 2-pyridylmethyl are most especially preferred.

In the case of the more preferred compounds of Formula I wherein Arrepresents 3-, 4-, or 5-pyrazolyl, Ar can be depicted as the formula##STR6## wherein R² and R³ independently represent each of thesubstituents (with each of the listed exceptions) noted in the Summaryof the Invention and in the foregoing discussions and R⁹ representshydrogen or C₁ -C₆ alkyl. Preferred compounds of this type include thosewherein R² and R³ each independently represents H, C₁ -C₄ alkyl, benzyl,F, Cl, Br, I, NO₂, CF₃, OCF₃, C₁ -C₄ alkoxy, C₁ -C₁₀ alkoxycarbonyl, C₃-C₆ alkenyloxycarbonyl, benzyloxycarbonyl, or amino-, C₁ -C₄ alkylamino-or di C₁ -C₄ alkylaminocarbonyl.

The substituents on the triazolopyrimidine fragment of Formula I arerepresented by X, Y, and Z. Substituents X, Y, and Z independentlyrepresent hydroxyl, carboxyl, hydrogen, C₁ -C₆ alkyl, C₁ -C₆ mono- orpolyhaloalkyl, C₁ -C₆ alkoxy, C₁ -C₆ mono- or polyhaloalkoxy, amino, C₁-C₄ alkylamino, di C₁ -C₄ alkylamino, phenyl (optionally substituted witone or more groups chosen from F, Cl, Br, I, nitro, C₁ -C₆ alkyl, or C₁-C₆ mono- or polyhaloalkyl), C₁ -C₆ alkylthio, halogen, or two adjacentsubstituents (i.e. X and Y or Y and Z) are joined together to form asaturated five, six, or seven-membered saturated cyclic structure ofcarbon atoms or up to one heteroatom chosen from among nitrogen, oxygen,or sulfur (i.e. X,Y or Y,Z is --(CH₂)_(n) -- wherein n is 3, 4, or 5; orX,Y or Y,Z is --(CH₂)_(n) --A--(CH₂)_(m) -- wherein n is 0-4, the valueof m is equal to the ring size minus (n+3) and A is NH, O, or S).

Compounds of Formula I wherein X, Y, and Z independently represent H, F,Cl, Br, I, C₁ -C₄ alkyl, C₁ -C₄ alkoxy, C₁ -C₄ alkylthio, C₁ -C₄haloalkyl are preferred.

The most highly preferred compounds of the invention are those compoundsof Formula I wherein X represent H, CH₃, CF₃, OCH₃, OC₂ H₅, or SCH₃ ; orY represents H, Cl, or CH₃ ; or Z represents H, CH₃, or OCH₃ ; and Arrepresents substituted phenyl wherein R¹ represents F, Cl, Br, CF₃, NO₂,or C₁ -C₄ alkoxycarbonyl; or R² represents H or CH₃ ; or R⁵ representsH, F, Cl, Br, OCH₃, or CH₃ ; and R³ and R⁴ represent hydrogen and theiragriculturally acceptable salts. Additional most highly preferredcompounds are those compounds of Formula I wherein X or Y or Z are asdefined above and Ar represents 3-, 4-, or 5-pyrazolyl wherein R⁹represents H, CH₃, or C₂ H₅ ; or R² and R³ independently represent H,CH₃, CF₃, or C₁ -C₄ alkoxycarbonyl and their agriculturally acceptablesalts.

The substituent V of Formulae I and II represents any of the following:hydrogen, alkyl, alkenyl, alkynyl, phenylalkyl, substituted phenylalkyl,alkanoyl, alkoxycarbonyl, phenoxycarbonyl, dialkylaminocarbonyl,alkylsulfonyl, phenylsulfonyl, alkylthiocarbonyl, or phenylthiocarbonylwherein alkyl, alkenyl, and alkynyl are as defined above and each phenylgroup is optionally substituted as defined above.

Preferred derivatives of the invention are those compounds of Formula Iwherein V represents hydrogen, C₁ -C₄ alkyl, allyl, benzyl, --COR¹³,--CO₂ R¹³, --CONR¹³ R¹³, --CSOR¹³, and --SO₂ R¹³, wherein R¹³ is C₁ -C₆alkyl, phenyl (optionally substituted by one or more groups chosen fromhalo, C₁ -C₆ alkyl, or C₁ -C₆ haloalkyl), or C₁ -C₂ haloalkyl.

The more preferred derivatives of the invention with respect to V arethose wherein V represents hydrogen, C₁ -C₄ alkyl, allyl, benzyl, C₂ -C₄alkanoyl, C₂ -C₃ haloalkanoyl, benzoyl, C₁ -C₄ alkoxycarbonyl,phenoxycarbonyl, di C₁ -C₄ alkylaminocarbonyl, C₁ -C₄alkoxythiocarbonyl, C₁ -C₄ alkylsulfonyl, C₁ -C₂ haloalkylsulfonyl, orphenylsulfonyl, each phenyl optionally substituted by one or more groupschosen from among halo, nitro, methyl, and trifluoromethyl. The mostpreferred compounds in this regard are those wherein V representshydrogen, C₂ -C₄ alkanoyl, C₁ -C₄ alkoxycarbonyl, or di C₁ -C₄alkylaminocarbonyl.

Substituted 1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonamides and theirtetrahydro derivatives behave as acids due to the presence of asulfonamide moiety proton and consequently form salts when treated withbases. The term "agriculturally acceptable salts" is employed in thisapplication to denote compounds wherein the acidic sulfonamide proton ofthe compounds of Formulae I and II and replaced by a cation which is notherbicidal, especially to crop plants, nor significantly deleterious tothe applicator, the environment, or the ultimate user of any crop beingtreated. Suitable cations include, for example, those derived fromalkali or alkaline earth metals and those derived from ammonia andamines. Preferred cations include sodium, potassium, magnesium, andaminium cations of the formula

    R.sup.10 R.sup.11 R.sup.12 NH.sup.⊕

wherein R¹⁰, R¹¹, and R¹² each, independently represents hydrogen or C₁-C₁₂ alkyl, C₃ -C₁₂ cycloalkyl, or C₃ -C₁₂ alkenyl, each of which isoptionally substituted by one or more hydroxy, C₁ -C₈ alkoxy, C₁ -C₈alkylthio or phenyl groups. Additionally, any two of R¹⁰, R¹¹, and R¹²together represent an aliphatic difunctional moiety containing 1 to 12carbon atoms and up to two oxygen or sulfur atoms. Sodium, potassium,ammonium, and triethanolaminium are most preferred cations.

Specifically preferred compounds include the compounds of Formula Igiven in the following examples and, except for examples 38 and 39,their agriculturally acceptable salts.

1.5,7-Dimethyl-N-(2,6-dichlorophenyl)-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonamide

2.5-Methyl-N-(2,6-dichlorophenyl)-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonamide

3.5-Methyl-N-(2-bromo-6-chlorophenyl)-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonamide

4.5-Methyl-N-(2,6-difluoro-3-methylphenyl)-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonamide

5.5-Methyl-N-(2,6-difluorophenyl)-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonamide

6.5,7-Dimethoxy-N-(2,6-dichloro-3-methylphenyl)-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonamide

7.5,7-Dimethoxy-N-(2-methoxy-6-trifluoromethylphenyl)-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonamide

8.5-Methyl-7-methylthio-N-(2,6-dichlorophenyl)-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonamide

9.5-Methyl-7-methylthio-N-(2-trifluoromethylphenyl)-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonamide

10.7-Ethoxy-5-methyl-N-(2,6-dichloro-3-methylphenyl)-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonamide

11.5,7-Dimethyl-N-(2-chloro-6-phenylphenyl)-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonamide

12.5-Methyl-N-(2-methyl-6-nitrophenyl)-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonamide

13.5-Methyl-N-(2-chloro-6-methylphenyl)-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonamide

14.6-Methyl-N-(2-bromo-6-methylphenyl)-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonamide

15.6-Methyl-N-(2-fluoro-6-chlorophenyl)-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonamide

16.6-Methyl-N-(2-chloro-6-methylphenyl)-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonamide

17.6-Methyl-N-(2-methyl-6-nitrophenyl)-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonamide

18.7-Ethoxy-5-methyl-N-(2-trifluoromethylphenyl)-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonamide

19.7-Methoxy-5-methyl-N-(2,6-dichloro-3-methylphenyl)-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonamide

20.7-Ethoxy-5-methyl-N-(2-bromo-6-chloro-3-methylphenyl)-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonamide

21.5,7-Dimethoxy-N-(2,6-dibromo-3-methylphenyl)-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonamide

22. Methyl3-methyl-N-(5,7-dimethyl-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonyl)anthranilate.

23. Methyl3-methyl-N-(7-ethoxy-5-methyl-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonyl)anthranilate.

24. Methyl3-fluoro-N-(6-chloro-1,2,4-triazolo[1,5-a]-pyrimidine-2-sulfonyl)anthranilate.

25.5,7-Dimethoxy-N-(2,6-dichlorophenyl)-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonamide.

26.7-Methyl-N-(2,6-dichlorophenyl)-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonamide.

27.N-(2,6-dichlorophenyl)-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonamide.

28.7-Ethoxy-5-methyl-N-(2,6-dibromo-3-methylphenyl)-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonamide.

29.6-Chloro-N-(2,6-difluorophenyl)-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonamide.

30.5-Methyl-7-trifluoromethyl-N-(2-methoxy-6-trifluoromethylphenyl)-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonamide.

31.5,7-Dimethyl-N-(1,3-dimethyl-5-trifluoromethyl-4-pyrazolyl)-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonamide.

32.5-Methyl-N-(1,3-dimethyl-5-trifluoromethyl-4-pyrazolyl)-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonamide.

33.5,7-Dimethyl-N-(1-methyl-4-ethoxycarbonyl-4-pyrazolyl)-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonamide.

34.5,7-Dimethoxy-N-(2-chloro-1-naphthyl)-1,2,4-triazolo-[1,5-a]pyrimidine-2-sulfonamide.

35.5-Methyl-N-(2-chloro-1-naphthyl)-1,2,4-triazolo-[1,5-a]pyrimidine-2-sulfonamide.

36.5-Methyl-7-methoxy-N-(2-chloro-1-naphthyl)-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonamide.

37.5-Methyl-7-ethoxy-N-(2-chloro-1-naphthyl)-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonamide.

38.5-Methyl-N-(2-methylpropanoyl)-N-(2,6-difluorophenyl)-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonamide.

39.5-Methyl-N-acetyl-N-(2,5-dichlorophenyl)-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonamide.

Specially preferred compounds of Formula II include the following andtheir agriculturally acceptable salts:

1.5,7-Dimethyl-N-(2,6-dichlorophenyl)-4,5,6,7-tetrahydro-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonamide

2.5-Methyl-N-(2,6-dichlorophenyl)-4,5,6,7-tetrahydro-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonamide

3.5,7-Dimethyl-N-(2-trifluoromethylphenyl)-4,5,6,7-tetrahydro-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonamide

Furthermore, in the compounds corresponding to general Formula II, theexistence of stereoisomerism is possible. For example, stereoisomericrelationships exist when at least one of substituents X, Y, and Z doesnot equal hydrogen. When only one of substituents X, Y, and Z does notequal hydrogen, the compound of Formula II may exist as a mixture ofenantiomers. One enantiomer will be designated as having theR-configuration and the other will be designated as having theS-configuration. Each enantiomer may exhibit different levels ofherbicidal activity. When two or more of substituents X, Y, or Z inFormula II do not equal hydrogen, the material may exist as a mixture ofdiastereomers. For example, when two substituents among X, Y and Z donot equal hydrogen, the compound may exist as two diastereomers. Whenall three of substituents X, Y and Z do not equal hydrogen the compoundmay exist as four diastereomers. In addition all of the diastereomersdescribed above exist as a mixture of two enantiomers. All of thestereoisomers described above, diastereomers and their enantiomericpairs, may exhibit different levels of herbicidal activity.

The synthesis of compounds of general Formula I can be carried out in astraightforward manner as illustrated in Scheme I. Reaction of asulfonyl chloride of Formula IV with the appropriate aromatic(substituted or unsubstituted) or heteroaromatic (substituted orunsubstituted) amino compound (ArNH₂) under basic conditions yields thedesired product of Formula I. A wide range of solvents may be employed(i.e., CH₂ Cl₂, CH₃ CN or pyridine) at temperatures ranging from 0° C.to reflux. Bases which serve as catalysts include pyridine,4-dimethylaminopyridine and tertiary alkylamines such as triethylamineor N-methylmorpholine. Generally the amino compound serves as thelimiting reagent. Molar ratios of between 1.1 and 1.0 for the sulfonylchloride to amino compound and molar ratios of between 5.0 and 1.1 forthe base to amino compound are used most often. A wide range ofconcentrations may be employed (i.e., 0.1-5M). Generally concentrationsin the range of 0.5-2M are used to give a homogeneous reaction whichproceeds at a convenient rate. In addition it is sometimes advantageousto use a combination of pyridine derived base catalysts and tertiaryamine bases. The use of pyridine as a solvent is convenient as thepyridine can serve both as the solvent and the catalyst in thetransformation. ##STR7##

An alternative route to compounds of Formula I is also illustrated inScheme I. In cases where the amino compound (ArNH₂) is less reactive(less nucleophic) is it advantageous to prepare a metal derivative ofthe amino compound by treatment with a strong base. The metalderivatives are generally prepared in ether solvents (i.e., THF) usingstrong bases such as alkali metal alkyls (i.e., n-BuLi) or alkali metalhydrides (i.e., NaH or KH) at temperatures ranging from -80° C. to 0° C.The amide anion thus generated in situ can be reacted with a sulfonylchloride of Formula IV to yield the desired product of Formula I.Generally, molar ratios of the starting amino compound to sulfonylchloride of 2 to 3 are used to ensure complete reaction

The method of U.S. application Ser. No. 795,818, filed on Nov. 11, 1985,which method employs the condensation of N-trialkylsilylanilines withsulfonyl chlorides of Formula IV to produce compounds of Formula I, canalso be used and is especially valuable in laboratory operations.

Sulfonyl chlorides of Formula IV represent key intermediates in thesynthesis of sulfonamides of Formula I. Sulfonyl chlorides of Formula IVmay be prepared according to routes outlined in Scheme II. Mercaptans ofFormula V may be converted to sulfonyl chlorides of Formula IV bytreatment with chlorine in an aqueous acidic medium. Generally themedium would be aqueous acetic acid or aqueous HCl. The temperature ofthe reaction mixture is generally maintained between -20° C. and 25° C.during the course of the chlorine addition. Most preferably, temperatureranges between -20° C. and 0° C. are employed to minimize unwanted sidereactions such as hydrolysis of the compound of Formula IV to thecorresponding sulfonic acid. Alternatively, the mercaptan of Formula Vmay be suspended in a two phase system of aqueous acid (i.e., HCl) andan organic solvent (i.e., CH₂ Cl₂) and treated with sodium hypochlorite.This serves to convert the mercaptan to the sulfonyl chloride in areproducibly good yield. The solubility of the product in the organicphase serves to protect it from hydrolysis to the sulfonic acid. Again,temperatures in the range of -20° C. to 25° C. are employed withtemperatures in the range of -5° C. to 5° C. being most generally used.##STR8##

As an alternative, it is sometimes preferred to prepare sulfonylchlorides of Formula IV from benzyl sulfides of Formula VI (Scheme II).Reaction conditions as described above for the conversion of mercaptansto sulfonyl chlorides are operable. This procedure yields by-productscontaining benzyl residues which are generally removed by washing theproduct with water and/or an appropriate organic solvent and drying invacuo.

Compounds of general Formulae V or VI may be prepared by routesillustrated in Scheme III. Some derivatives of Formulae V and VI areknown materials (i.e., V: X=Z=Me,Y=H and VI: X=Z=Me,Y=H) prepared bymethods described in J. Med. Chem., 25, 420 (1982). Compounds of FormulaV are prepared directly by reaction of a 1,3-diketone with commerciallyavailable 3-amino-5-mercapto-1,2,4-triazole of Formula VII in glacialacetic acid as a solvent. Generally the reaction is performed at reflux.Alternatively, the compound of Formula VII may be benzylated with benzylchloride using an alkali earth metal alkoxide (i.e., NaOH) as a base toyield the known benzyl sulfide of Formula VIII (J. Heterocycl. Chem.,12, 1187 (1975)). The benzyl sulfide of Formula VIII can be condensedwith not only 1,3-diketones but also β-keto esters, malonic esters,malonaldehyde, β-ketoaldehydes or α-formyl esters or derivatives thereof(i.e., acetals or enol ethers) to yield products of Formula VI asillustrated in Table A. Generally these reactions can be carried outunder acidic conditions (i.e., glacial acetic acid as a solvent) orbasic conditions (i.e., NaOR in ROH wherein R is C₁ to C₄ alkyl). Incases where the X, Y and Z substituents in Formula VI are derived from a1,3 -diketone, compounds of Formula VI may be prepared by benzylation ofNaOH) and benzyl chloride in a variety of solvents (i.e., water,methanol, ethanol, THF, dioxane, acetonitrile, DMF or DMSO orcombinations of the aforementioned). ##STR9##

                  TABLE A                                                         ______________________________________                                        1,3-Dicarbonyl           Compound of                                          Compound or   Reaction   Formula V or VI                                      Derivative    Conditions X       Y     Z                                      ______________________________________                                                      acid       R       R'    R"                                      ##STR10##    acid       H       R'    R                                       ##STR11##    base       R       R'    H                                       ##STR12##    acid       OH*     R'    R                                       ##STR13##    acid       H       H     H                                       ##STR14##    base       OH      R'    OH                                     ______________________________________                                         *In this structural representation, as well as others bearing OH groups a     5 or 7positions of the 1,2,4triazolo[1,5-a]pyrimidine, the enol form has      been depicted. Clearly this is the equilibrium with the various keto          forms.                                                                   

In instances where the 1,3-dicarbonyl compound is unsymmetrical, thepossibility of obtaining two different isomers from condensation withCompound VIII exists. In general, under acidic conditions the exocyclicnitrogen in Compound VIII is the first to condense with the1,3-dicarbonyl compound. Under basic conditions the endocyclic nitrogenin Compound VIII is sometimes more reactive. Consequently, in situationswhere a clear difference in reactivity of the two carbonylfunctionalities in the 1,3-dicarbonyl compound exists, some measure ofregiochemical control may be achieved by choice of reaction conditions(i.e., entries 2 and 3 in Table I).

To prepare the alternative regioisomer to that depicted in entry 4 inTable A (i.e., VI: X═R, Y═R', and Z═OH) a route illustrated in Scheme IVwas followed. Compound VIII was condensed with2,3-dibromoalkylcarboxylic acid esters to yield a compound of Formula VI(VI: X═R, Y═R', Z═OH). The reaction is generally carried out inrefluxing pyridine. ##STR15##

An additional route to compounds of Formula VI involves condensation ofCompound VIII with methanaminium compounds of Formula IX as illustratedin Scheme V. The condensation is usually carried out by reaction inrefluxing glacial acetic acid and is useful in the synthesis of a numberof 6-substituted 1,2,4-triazolo[1,5-a]pyrimidines. ##STR16##

In the synthetic routes listed above, compounds of Formula VI where Xand/or Z is OH are capable of undergoing further transformation (SchemeVI). For example, treatment of a compound of Formula VI (X and/or Z═OH)with phosphorus oxychloride yields the corresponding compound of FormulaVI (X and/or Z═Cl). The reaction is generally carried out at reflux inneat phosphorus oxychloride or with phosphorous oxychloride in a solvent(i.e., acetonitrile). Compounds of Formula VI (X and/or Z═Cl) can befurther reacted with nucelophiles (i.e., NaOCH₃, MeMgBr) to yieldcompounds of Formula VI (X and/or Z═OCH₃ or CH₃, respectively). Inaddition, compounds of Formula VI (X and/or Z═Cl) may be reduced toafford other compounds of Formula VI (X and/or Z═H). An effectivereducing agent for this type of transformation is zinc-copper couple inthe presence of acid. ##STR17##

Other compounds of the present invention are best prepared in a mannerillustrated in Scheme VII. Compounds such as are represented by FormulaXI wherein X¹ and Z¹ are independently represented by hydrogen, C₁ -C₄alkyl, alkylthio, arylthio, or amino (including mono- and disubstitutedalkylamino), can be prepared by this method. The method involves thereaction of a compound of Formula X wherein X and Z independentlyrepresent hydrogen, C₁ -C₄ alkyl or an appropriate leaving group with anucleophile in a suitable solvent. This procedure effects thesubstitution of the leaving group by the nucleophilic unit. Arepresentative leaving group that is effective in this process istrifluoroethoxide (^(-OCH) ₂ CF₃). Representative nucleophiles for thisprocess include alkali metal salts of alkyl mercaptans, alkali metalsalts of aryl mercaptans, ammonia, primary and secondary alkylamines,and alkali metal salts of hydroxides. These nucleophiles result in thedisplacement of the leaving group (X and/or Z) in Formula X to produce acompound of Formula XI containing X¹ and/or Z¹ represented as alkylthio,arylthio, amino, mono- and disubstituted alkylamino, or hydroxyl,respectively. Suitable solvents for this transformation include polaraprotic solvents (i.e., DMSO, DMF), alcohols and water. Suitablereaction temperatures range from 0° C. to 100° C. although thetemperature of the reaction is usually not critical. Reactiontemperatures of 20° C. to 30° C. are most frequently employed. ##STR18##

In addition certain compounds of the present invention containing ahalogen in the 6-position on the 1,2,4-triazolo[1,5-a]pyrimidine ringsystem may be prepared by halogenation of the corresponding6-unsubstituted compound. This is illustrated in Scheme VIII. Ingeneral, N-halo-succinimide derivatives are the halogenating agents ofchoice. The reactions are often performed in acid solvents attemperatures ranging from room temperature to 150° C. ##STR19##

Another method to prepare the compounds of the present invention isillustrated in Scheme IX. Compounds of general Formula I can be oxidizedto yield compounds of Formula XII. Oxidizing agents capable of thistransformation include various transition metal oxidants such asderivatives of hexavalent chromium (Cr^(VI)) or heptavalent manganese(Mn^(VII)), organic peracids or peroxides. Oxidizing agents such aspotassium permanganate, chromium trioxide, peracetic acid and hydrogenproxide are frequently employed. Preferred conditions for the conversionof compounds of Formula I to compounds of Formula XII involve reactionof the former with two to five molar equivalents of potassiumpermanganate in 0.1N to 1.0N aqueous alkali metal hydroxide (i.e., NaOHor KOH) as a solvent. The reaction may be run at temperatures rangingfrom ambient temperature to reflux. Most commonly the reaction is run at50° C. to 60° C. The product of this reaction (Formula XII) can behydrolyzed to a compound of Formula XIII by treatment with aqueous acidin an organic co-solvent. Typical acids include hydrochloric acid,sulfuric acid, acetic acid, trifluoroacetic acid or methanesulfonicacid. Appropriate organic co-solvents include acetone, methyl ethylketone, ethanol, acetonitrile or tetrahydrofuran. Lastly, compounds ofFormula XIII can be reconverted to a compound of general Formula I bycyclization with a 1,3-dicarbonyl compound or an equivalent of a1,3-dicarbonyl compound. The conditions for this cyclization, thestructural requirements for the 1,3-dicarbonyl compound or an equivalentand structural considerations for the product are as describedpreviously for the conversion of compounds of Formulae VII and VIII tocompounds of Formula V and VI. ##STR20##

The method for the preparation of compounds of Formula I as illustratedin Scheme IX is employed advantageously in certain situations. Variusfunctional groups present on the 1,2,4-triazolo[1,5-a]pyrimidine ringsystem (X, Y and Z) of Formula I which impart useful herbicidal activitycan only be produced in low yield by previously described routes. Theprimary cause for the low yield in the previously described routes isthe incompatability of the function group or the ring system which bearsthe functional group to the conditions required to form the requiredsulfonyl chlorides of Formula IV. Examples of substituents (X, Y and Z)present in compounds of Formula I which are advantageously prepared bythe method outlined in Scheme IX include H, halo (F, Cl, Br and I),hydroxy, C₁ -C₄ alkyl, C₁ -C₄ alkoxy, C₁ -C₄ alkylthio, C₁ -C₄alkylsulfinyl, C₁ -C₄ alkylsulfonyl, C₁ -C₄ mono- or polyhaloalkyl, C₁-C₄ mono- or polyhaloalkoxy, C₁ -C₄ polyhaloalkylthio, C₁ -C₄polyhaloalkylsulfinyl, C₁ -C₄ polyhaloalkylsulfonyl, amino, C₁ -C₄ mono-or dialkylamino, phenyl, substituted phenyl, phenoxy, substitutedphenoxy, phenylthio, phenylsulfinyl, phenylsulfonyl, substitutedphenylthio, substituted phenylsulfinyl, substituted phenylsulfonyl,carboxyl, and carboxyl derivatives such as esters derived from C₁ -C₄alcohols. The substituents X and Y or Y and Z can also be joined to forma ring containing a total of five to seven atoms. This ring may containheteroatoms (i.e., nitrogen, oxygen or sulfur), unsaturation (i.e.,--CO-- or --C═C--) or a halogen substituent.

The compounds of Formula I which are most advantageously prepared by themethod outlined in Scheme IX contain substituents (X, Y and Z) which areone or more of the following: H, halo (F, Cl, Br and I), C₁ -C₄ alkyl,C₁ -C₄ alkoxy, C₁ -C₄ alkylthio, C₁ -C₄ alkylsulfinyl, C₁ -C₄alkylsulfonyl, C₁ -C₄ mono or polyhalogalkyl, C₁ -C₄ mono- orpolyhaloalkoxy, C₁ -C₄ polyhaloalkylthio, C₁ -C₄ polyhaloalkylsulfinyl,C₁ -C₄ polyhaloalkylsulfonyl, amino and C₁ -C₄ mono- or dialkylamino.

Specifically preferred substituent patterns of Formula I which may beprepared by the method outlined in Scheme IX are the following:

1. X═Y═Z═H

2. X═CF₃, Y═H and Z═CH₃

3. X═Z═CF₃ and Y═H

4. X═Cl, Y═H and Z═CH₃

5. X═OCH₃, Y═H and Z═CH₃

6. X═OC₂ H₅, Y═H and Z═CH₃

7. X═SCH₃, Y═H and Z═CH₃

The starting material of Formula I in the reaction sequence of Scheme IXmay contain one or more of the following substituents: H, halo (F, Cl,Br and I) and C₁ -C₄ alkyl. The aromatic ring in these startingmaterials and intermediates is defined as described previously forFormula I. The R group in intermediates of Formula XII may be H or CH₃.

Compounds of the present invention represented by Formula I wherein V isR are derived from compounds represented by Formula I wherein V is H asillustrated in Scheme X. The derivatization procedure involves treatmentof compounds of Formula I wherein V is H with a base in a suitablesolvent followed by the introduction of an appropriate electrophilicderivatizing reagent. From this process compounds of Formula I wherein Vis R can be isolated in good yields. Suitable bases include tertiaryalkylamines (i.e., triethylamine), pyridine, 4-dimethylaminopyridine,alkali metal carbonate (i.e., sodium carbonate or potassium carbonate)and alkali metal alkoxides (i.e., sodium ethoxide or potassiumt-butoxide). Suitable solvents include ethers (i.e., tetrahydrofuran),pyridine, acetone, acetonitrile, alcohols (i.e., methanol, ethanol,isopropanol and t-butanol) and polar aprotic solvents (i.e., DMSO andDMF). Suitable electrophilic reagents include alkyl halides, arylalkylhalides (i.e., benzyl chloride), carboxylic acid chlorides, alkylchloroformates, aryl chloroformates, N,N-dialkylcarbamoyl chlorides,alkylsulfonyl chlorides arylsulfonyl chlorides, alkyl chlorothioformates##STR21## and aryl chlorothioformates ##STR22##

Agriculturally acceptable salts of the compounds of Formula I can beprepared by treatment of compounds of Formula I with a metal hydroxidesuch as sodium hydroxide, potassium hydroxide, or magnesium hydroxide,or an amine such as ammonia, dimethylamine, triethylamine,triethanolamine, diallylamine, 2-butoxyethylamine, morpholine,cyclododecylamine, or benzylamine. The reactions are typically carriedout in a solvent in which one or more of the compounds of Formula I, thebase, and the agriculturally acceptable salt product has appreciablesolubility. Water is a preferred solvent. The agriculturally acceptablesalts can be recovered from the reaction mixtures obtained byconventional means such as filtration or evaporation of the volatilecomponents, or the reaction mixtures can be used without isolation.

In typical operations, a compound of Formula I is placed in water orother suitable solvent and an approximately equimolar quantity or anexcess of base is added. The solution obtained is combined withagriculturally acceptable adjuvants and used as a herbicide.

The salts of this invention are additionally useful for purifying thecompounds of Formula I. In typical operations, a contaminated compoundof Formula I is combined with an excess of base in water to obtain asolution of the salt. Water insoluble contaminants are then removed byfiltration or extraction with an immiscible organic solvent, such asmethylene chloride or ether, and the compound of Formula I isregenerated by the addition of an acid and recovered by filtration,centrifugation, or the like. Sodium hydroxide and ammonium hydroxide arepreferred bases and hydrochloric acid a preferred acid in theseprocedures.

Compounds of the present invention represented by Formula II are alsoderived from compounds represented by Formula I as illustrated in SchemeXI. the general process involves the reduction of compounds of generalFormula I with an appropriate reducing agent in a suitable solvent toyield compounds of general Formula II. Reducing agents which areeffective include metal hydrides (i.e., sodium borohydride) in thepresence of acids (i.e., methanesulfonic acid) and hydrogen in thepresence of a normal hydrogenation catalyst (i.e., palladium on carbon).For reductions with metal hydrides, polar aprotic solvents (i.e., DMSO)are most frequently used. For reductions using hydrogen and a catalyst,alcohols (i.e., ethanol) are most frequently employed as solvents.##STR23##

The majority of the amino compounds (ArNH₂) utilized to prepare thecompound of the present invention as illustrated in Scheme I wereobtained from commercial sources or prepared by known literatureprocedures or minor modifications of literature procedures. Others arenovel compounds made by novel processes.

A number of the amino compounds (ArNH₂) used to prepare the compounds ofthe present invention are derivatives of anthranilic acid. Many of thesecompounds can be prepared according to conventional methods described byS. J. Holt et al., Royal Soc. Proc. Sec. B, 148, 481 (1958), P. W.Sadler et al., J. Am. Chem. Soc., 78, 1251 (1956), and G. Reissenweberet al., U.S. Pat. No. 4,310,677 (1982). Other anthranilic acidderivatives can be prepared by standard derivatizations (i.e.,conversion to esters and amides) of known substituted or unsubstituted2-nitrobenzoic acids followed by reduction of the nitro group asrepresented in Scheme XII. ##STR24##

A number of the amino compounds are prepared by reduction of anthranilcacids or esters and subsequent derivatization of the reduction product.This is outlined in Scheme XIII. The carbinol reduction products may bederivatized by reaction with base and various electrophiles (i.e., alkylhalides and carboxylic acid chlorides). ##STR25##

A large number of the amino compounds utilized in the preparation of thecompounds of this invention contain halogen substituents ortho to theamino group. Many of these compounds were prepared by halogenation ofthe corresponding material bearing no substituent in the ortho positionaccording to a general procedure described by R. S. Neale et al., J.Org. Chem., 29, 3390 (1964). The starting materials for thesehalogenations are commercially available or known in the literature(i.e., British Pat. No. 695,164 (1953); D. S. Noyce et al., J. Org.Chem. 26, 1732 (1961) and U.S. Pat. No. 3,813,234 (1974)). In certaininstances to facilitate the transformation and insure ortho selectivityin the halogenation process the starting materials for the halogenationwere acetamide derivatives (ArNHCOCH₃) or derivatives containing groups(i.e., Br) which would block halogenation at other positions in themolecule (i.e., para to the amino group). Following halogenation theacetamide derivatives were hydrolized back to the desired amino compoundand the blocking groups were removed (i.e., Br in the para position wasselectively removed by reduction in the presence of Cl in the orthoposition). Other chlorine and bromine substituted amino compounds wereprepared by known procedures (i.e., U.S. Pat. No. 4,188,342 (1980); C.R. Rasmussen et al. J. Med. Chem., 21, 1044 (1978); H. E. Dadswell etal. J. Chem. Soc., 1102 (1927); U.S. Pat. No. 3,813,234 (1974) and P. B.D. DeLaMare and J. H. Ridd, "Aromatic Substitution, Nitration andHalogenation", Academic Press, New York (1959), p. 106.

A number of the amino compounds used as starting materials for thecompounds of this invention contain sulfur substituents in the orthoposition. These were prepared using known procedures (i.e., R. R. Guptaet al Heterocycles, 16, 1527 (1981) and J. P. Chupp et al., J. Org.Chem., 49, 4711 (1984)). In some cases alkylthio groups were present andthese were synthesized by alkylation of the corresponding mercaptan.Compounds having alkyl or aryl sulfinyl or sulfonyl groups weresynthesized by oxidation of the appropriate alkyl or arylthio groups.

Some starting amino compounds containing amino, alkylamino, aryloxy orpyridyloxy groups were prepared by catalytic reduction of thecorresponding nitro compounds. The amino, alkylamino, aryloxy orpyridyloxy group were usually introduced via displacement of a leavinggroup ortho to the nitro group in the requisite nitrobenzene.

Other starting amino compounds were prepared by procedures involvingmetalation of the aromatic ring of N-substituted derivatives (i.e.,t-butoxycarbonyl derivatives) of an aromatic amino compound followed bythe resulting organometallic reagent with an electrophile. This generalprocedure is described in H. Gschwend, Org. Reactions, Vol. 20, 1-360(1979) and is outlined in Scheme XIV. Suitable metalating agents areorganolithium reagents (i.e., n-butyl lithium or t-butyl lithium).Typical electrophiles include alkyl halides (i.e., methyl iodide, ethyliodide), aldehydes (i.e., formaldehyde, acetaldehyde), ketones (i.e.,acetone), alkyl or aryl sulfonyl halides (i.e., methylsulfonylchloride), and dialkyl or diaryl disulfides (i.e., dimethyl disulfide).These electrophiles are useful for the introduction of alkyl,hydroxyalkyl and alkylthio and arylthio groups to the position ortho tothe amino group. After the reaction of the organometallic intermediatewith the electrophile the nitrogen substituent is removed by hydrolysis.##STR26##

Other aromatic amino compounds used to prepare compounds of the presentinvention are prepared by conversion of carboxylic acid groups orderivatives of carboxylic acid groups to amino groups by standardmethodology. Such a transformation is illustrated in Scheme XV anddescribed in J. Royal. Netherlands Chem. Soc., 97, 53 (1978). ##STR27##

Other amino compounds such as those which are heteroaromatic aminocompounds are prepared by known procedures such as those described inRec. Trav. Chim., 69, 673 (1950), T. Talik et al., Chem. Abstracts, 59:8698a (1963) and L. C. Behr and R. Fusco In "Heterocyclic Compounds", A.Weissberger, Ed. Vol 22, Interscience Publishers, New York (1967), pp.3-174 or straightforward modification of the art described above.

Other amino compounds used to prepare compounds of the present inventionare prepared by direct metalation of the aromatic ring. This isillustrated schematically in Scheme XVI. An aromatic ring bearing one tothree substituents on the ring may be metalated with an alkyl lithiumreagent (i.e. n-butyl lithium, s-butyl lithium or t-butyl lithium) toform an aryl lithium intermediate. This reaction is most frequentlycarried out in an ethereal solvent (i.e. diethyl ether, tetrahydrofuranor 1,2-dimethoxyethane) at temperature ranging from 78° C. to ambienttemperature. It is sometimes advantageous to perform the metalationreaction in the presence of additives such astetramethylethylenediamine. The aryl lithium reagent is generated insitu and is reacted with carbon dioxide followed by protonation of theresultant carboxylate to form the carboxylic acid. The carboxylic acidcan then be converted to the corresponding amino compound by standardmethodology of the Hoffman, Curtius, Lossen and Schmidt reactions.##STR28##

The substituents (R¹, R², and R⁵) which are operable in the processillustrated in Scheme XVI are as follows: R¹, R², and R⁵ may be chosenfrom among H, F, Cl, Br, I, C₁ -C₄ alkyl, C₁ -C₄ mono- or polyhaloalkylor C₁ -C₄ alkoxy. Most preferred substituents are R₂ is equal to H or C₁-C₄ alkyl; R¹ and R⁵ are equal to F, Cl, C₁ -C₄ mono- or polyhaloalkylor C₁ -C₄ alkoxy.

The intermediate carboxylic acid formed as illustrated in Scheme XVI orderivatives of the carboxylic acid (i.e. esters and amides) can beutilized to prepare other amino compounds which are useful in thepreparation of compounds of Formula I of the present invention. Thisprocess is illustrated in Scheme XVII. When the carboxylic acid productcontains a leaving group such as a F, Cl or Br atom at an adjacentposition, the carboxylic acid may be converted to a suitable derivativeand the halogen may then be replaced by displacement with a suitablenucleophile. Nucleophiles which are useful in this case include ammonia,C₁ -C₄ monoalkylamines, C₁ -C₄ dialkylamines, C₁ -C₄ alkali metalalkoxides, C₁ -C₄ alkali metal mono- or polyhaloalkoxides or C₁ -C₄alkali metal mercaptides. The use of these nucleophiles serves toreplace the halogen substituent with amino, C₁ -C₄ monoalkylamino, C₁-C₄ dialkylamino, C₁ -C₄ alkoxy, C₁ -C₄ mono- or polyhaloalkoxy or C₁-C₄ alkylthio respectively. The resultant products of the nucleophilicdisplacement can be converted to the corresponding amino compound bystandard methodology of the Hoffman, Curtius, Lossen and Schmidtreactions. ##STR29##

Other amino compounds which are useful in the preparation of compoundsof Formula I can be prepared as illustrated in Scheme XVIII. Thestarting material for this procedure is 2,6-difluoroaniline. The aminogroup of the aniline is protected with a silyl protecting groupaccording to a general procedure described by Magnus et al. inTetrahedron Lett., 1787 (1981) and Guggenheim et al. in TetrahedronLett., 1253 (1984). The protected aniline can then be metalated with analkyl lithium reagent (i.e. n-butyl lithium, s-butyl lithium or t-butyllithium) to form the corresponding aryl lithium reagent. The metalationis best carried out in ethereal solvents such as diethyl ether,tetrahydrofuran or dimethoxyethane at temperatures ranging from -78° C.to ambient temperature. It is sometimes advantageous to carry out themetalation in the presence of additives such tetramethylethylenediamine.The aryl lithium reagent is formed in situ and can be reacted with avariety of electrophilic reagents such as C₁ -C₄ alkyl halides, C₁ -C₄dialkyl disulfides or C₁ -C₄ alkyl sulfenyl halides, dimethylformamide,C₁ -C₄ acyl halides or C₁ -C₄ N-methyl-O-methyl alkylhydroxamates, C₁-C₄ alkyl chloroformates and carbon dioxide. These electrophilicreagents serve to introduce C₁ -C₄ alkyl, C₁ -C₄ alkylthio, formyl, C₁-C₄ acyl, C₁ -C₄ alkoxycarbonyl and carboxyl groups, respectively,directly into the 3-position of the aromatic ring. The product fromelectrophilic substitution can be deprotected using standard methodologyas described in the literature to form the desired amino compound.##STR30##

The table which follows contains a listing of some of the aromatic aminocompounds prepared by methods described above and not previouslydescribed in known art, which compounds are useful in the preparation ofthe biologically active compounds of this invention.

    ______________________________________                                         ##STR31##                                                                    Com-                                                                          pound     R.sup.1   R.sup.2   R.sup.3                                                                           R.sup.4                                                                           R.sup.5                                 ______________________________________                                        A    Cl             COOCH.sub.3                                                                             H   H   Cl                                      B    Br             COOCH.sub.3                                                                             H   H   CH.sub.3                                C    CH.sub.3       Cl        H   H   COOCH.sub.3                             D    Cl             CF.sub.3  H   H   Cl                                      C    Cl             H         H   H   CH.sub.2 OCH.sub.3                      E    Cl             H         H   H   CH.sub.2 OAc                            I    Cl             H         H   H   CH.sub.2 OCH.sub.2 Ph                         ##STR32##     H         H   H   H                                       K                                                                                   ##STR33##     H         H   H   H                                       L                                                                                   ##STR34##     H         H   H   F                                       M    F              H         H   H   SCH.sub.3                               N    CF.sub.3       H         H   H   OCH.sub.3                               O    CF.sub.3       H         H   H   N(CH.sub.3).sub.2                       P    CF.sub.3       H         H   H   OCH.sub.2 CH.sub.3                      Q    CF.sub.3       H         H   H   OCH.sub.2 CF.sub.3                      R    Br             CH.sub.3  H   H   Br                                      S    Br             CH.sub.3  H   H   Cl                                      ______________________________________                                    

The novel aniline compounds that are useful for the preparation ofcompounds of Formulae I and II can be described by the formula ##STR35##wherein (1) R¹ represents CF₃, R² represents hydrogen, and R⁵ representsC₁ -C₄ alkoxy, C₁ -C₄ polyfluoroalkoxy, or C₁ -C₄ alkylthio; (2) R¹ andR⁵ represent F and R² represents CH₃ or OCH₃ ; (3) R¹ and R⁵ representCl and R² represents CO₂ C₁ -C₄ alkyl, or CF₃ ; (4) R¹ represents F, R²represents hydrogen, and R⁵ represents C₁ -C₄ alkylthio or4-trifluoromethylphenoxy or 5-trifluoromethyl-2-pyridyloxy, eachoptionally containing up to two fluoro, chloro, or bromo substituents;(5) R¹ represents Cl, R² represents hydrogen, and R³ representshydroxymethyl, C₁ -C₄ alkoxymethyl, C₁ -C₄ alkanoyloxymethyl, orbenzyloxymethyl; (6) R² and R⁵ represent hydrogen and R¹ represents4-trifluoromethylphenoxy or 5-trifluoromethyl-2-pyridyloxy, eachoptionally containing up to two fluoro, chloro, or bromo substituents,(7) a C₁ -C₄ alkyl 3-amino-2-bromo-4-methylbenzoate; and (8) a C₁ -C₄alkyl 4-chloro-3-methylanthranilate.

Using the routes illustrated above or minor variations based on theprinciples illustrated above the novel compounds of this invention canbe prepared.

The invention is further illustrated by the following examples.

EXAMPLE 1 Preparation of5,7-dimethyl-2-mercapto-1,2,4-triazolo[1,5-a]pyrimidine

A solution of 10.1 g (0.0870 mol) of 3-amino-5-mercapto-1,2,4 triazole,8.71 g (0.0870 mol) of 2,4-pentanedione and 0.8 ml of piperidine in 300ml of HOAc was heated at reflux for 21.5 hours. After cooling to roomtemperature, the solid which separated was collected by filtration anddried in vacuo to yield 13.4 g of pale yellow needles, m.p. 245°-246° C.(decomposition); ¹ H NMR (DMSO-d₆ -CDCl₃) δ13.9 (1H, broad, SH), 7.19(1H, broad s, H in 6-position) 2.63 and 2.51 (3H each, s, CH₃ groups in5- and 7-positions), IR (KBr) ˜2680, 1628, 1560, 1400 and 1170 cm⁻¹. Ananalytical sample was prepared by recrystallization from acetic acid toyield colorless plates, m.p. 243.5°-244.5° C. (decomposition).

Analysis:

Calculated for C₇ H₈ N₄ S: C, 46.65, H, 4.47; N, 31.09;

Found: C, 46.34; H, 4.41; N, 30.82;

EXAMPLE 2 Preparation of2-benzylthio-5,7-dimethyl-1,2,4-triazolo[1,5-a]pyrimidine

Twenty percent NaOH (14.0 g, 70 mmol) was added dropwise to a suspensionof 11.5 g (64.0 mmol) of the mercaptan prepared in Example 1 in 125 mlof H₂ O over about 5 minutes. Benzyl chloride (7.4 ml, 8.1 g, 64 mmol)in 20 ml of CH₃ OH was added and the resulting mixture was vigoruslystirred at room temperature for 24 hours. The solid which beganseparating shortly after the addition of benzyl chloride was collectedby filtration and dried in vacuo to afford 16.1 g of white solid, m.p.134°-135° C. (lit m.p. 132°-134° C., T. Novinson et al, J. Med. Chem.,25, 420 (1982)): ¹ H NMR (CDCl₃) δ 7.1-7.6 (5H, m, Ph), 6.63 (1H, s, Hin 6-position), 4.50 (2H, s, --CH₂ S--), 2.67 and 2.58 (3H each, s, CH₃groups in 5- and 7-positions); IR (CHCl₃) 1620, 1447, 1339 and 1295cm⁻¹. 93% yield.

Analysis:

Calculated for C₁₄ H₁₄ N₄ S: C, 62.20; H, 5.22; N, 20.72.

Found: C, 62.21; H, 5.14; N, 20.89.

EXAMPLE 3 Preparation of2-benzylthio-6,7-cyclopentano-5-methyl-1,2,4-triazolo[1,5-a]pyrimidine

A solution of 51.6 g (0.250 mol) of 3-amino-5-benzylthio-1,2,4-triazoleand 31.5 g (0.250 mol) of 2-acetylcyclopentanone in 600 ml of HOAc washeated at reflux for 9.5 hours. The solvent was removed by evaporation,and the brown solid residue was recrystallized from EtOH to yield alight brown solid. A second recrystallization from EtOH gave 45.4 g (61percent) of the desired product as a light brown solid, m.p. 157°-158.5°C.: ¹ H NMR (CDCl₃) δ7.0-7.6 (5H, m), 4.51 (2H, s), 3.29 (2H, t), 2.97(2H, t), 2.0-2.7 (5H, m including s at 2.52); IR (CHCl₃) 1621, 1343 and1290 cm⁻¹.

Analysis:

Calculated for C₁₆ H₁₆ N₄ S: C, 64.84; H, 5.44, N, 18.90; S, 10.82.

Found: C, 64.88; H, 5.47; N, 18.98; S, 10.72.

EXAMPLE 4 Preparation of2-benzylthio-5,6,7-trimethyl-1,2,4-triazolo[1,5-a]pyrimidine

A solution of 51.6 g (0.250 mol) of 3-amino-5-benzylthio-1,2,4-triazoleand 28.5 g (0.250 mol) of 3-methyl-2,4-pentanedione in 350 ml of glacialacetic acid was heated at reflux for 17 hours. Upo cooling to roomtemperature, the reaction mixture was poured onto ice. The pale yellowsolid which separated was collected by filtration, washed with water anddried in vacuo to yield 67.1 g (94%) of the desired product as a paleyellow solid, m.p. 133.5°-135° C. The IR and ¹ H NMR spectra wereconsistent with the assigned structure.

Analysis:

Calculated for C₁₅ H₁₅ N₄ S: C, 63.35; H, 5.67; N, 19.70; S, 11.27.

Found: C, 63.07; H, 5.48; N, 19.71; S, 11.09.

EXAMPLE 5 Preparation of2-benzylthio-6-chloro-1,2,4-triazolo[1,5-a]pyrimidine

A solution of 6.52 g (31.6 mmol) of 3-amino-5-benzylthio-1,2,4-triazoleand 9.09 g (31.6 mmol) of 1,3-bis(dimethylamino)-2-chlorotrimethiniumperchlorate in 100 ml of glacial acetic acid was heated at reflux for 19hours. After cooling to room temperature, the solution was poured into300 ml of water. The solid which separated was collected by filtration,washed with water and dried in vacuo to yield 4.12 g (48%) of thedesired product as a brown solid, m.p. 119.5°-135° C. (decomposition).IR and ¹ H NMR spectra were consistent with the assigned structure.

Analysis:

Calculated for C₁₂ H₉ ClN₄ S: C, 51.90; H, 3.20; N, 20.24.

Found: C, 51.87; H, 3.42; N, 19.81.

EXAMPLE 6 Preparation of 2-benzylthio-1,2,4-triazolo-[1,5-a]pyrimidine

A solution of 2.0 g (9.6 mmol) of 3-amino-5-benzylthio-1,2,4-triazoleand 2.3 ml (9.6 mmol) of malonaldehyde bis(diethylacetal) in 20 ml ofglacial acetic acid was heated at reflux for 17 hours. After cooling toroom temperature, the solvent was removed by evaporation at reducedpressure. The brown solid residue was recrystallized from isopropylalcohol to afford 0.4 g (17%) of the desired product as a light browncrystalline solid, m.p. 104°-106° C. IR and ¹ H NMR spectra wereconsistent with the assigned structure.

Analysis:

Calculated for C₁₂ H₁₀ N₄ S: C, 59.52; H, 4.13; N, 23.13.

Found: C, 59.19; H, 4.09; N, 22.73.

EXAMPLE 7 Preparation of2-benzylthio-5-methyl-1,2,4-triazolo[1,5-a]pyrimidine

A solution of sodium ethoxide in EtOH was prepared by dissolving 0.54 g(24 mg-atoms) of sodium metal in 120 ml of anhydrous EtOH, and 10.0 g(48 mmol) of 3-amino-5-benzylthio-1,2,4-triazole was added. Afterstirring for 15 minutes at room temperature, 6.4 ml (6.35 g, 48.4 mmol)of acetylacetaldehyde dimethyl acetal dissolved in 100 ml of absoluteEtOH was was added dropwise. After the addition was complete thereaction mixture was stirred at room temperature for 68 hours. Theproduct which separated from solution was collected by filtration anddried to give 10.1 g (83%) of tan solid, m.p. 128.5°-130° C. IR and ¹ HNMR spectra were in agreement with the assigned structure.

Analysis:

Calculated for C₁₃ H₁₂ N₄ S: C, 60.94; H, 4.68; N, 21.86.

Found: C, 60.69; H, 4.61; N, 21.85.

EXAMPLE 8 Preparation of2-benzylthio-5-hydroxy-7-methyl-1,2,4-triazolo[1,5-a]pyrimidine

Ethyl 2,3-dibromobutyrate (1.33 g, 48.5 mmol) was added dropwise over 15minutes to a solution of 10 g (49 mmol) of3-amino-5-benzylthio-1,2,4-triazole in 20 ml of pyridine heated to 65°C. After the addition was complete, the reaction mixture was heated at65° C. for 20 hours, cooled to room temperature and filtered. Thefiltrate was concentrated by evaporation at reduced pressure. Theresidue was triturated with methanol to separate 1.64 g (13%) of thedesired product as a colorless crystalline solid, m.p. 219°-220° C. IRand ¹ H NMR spectra were in agreement with the assigned structure.

Analysis:

Calculated for C₁₃ H₁₂ N₄ OS: C, 57.37; H, 4.41; N, 20.60.

Found: C, 56.86; H, 4.41; N, 20.72.

EXAMPLE 9 Preparation of2-benzylthio-5-methoxy-7-methyl-1,2,4-triazolo[1,5-a]pyrimidine

A solution of 2.67 g (9.80 mmol) of2-benzylthio-5-hydroxy-7-methyl-1,2,4-triazolo[1,5-a]pyrimidine in 50 mlof phosphorous oxychloride was heated at reflux for 3 hours. The excessphosphorous oxychloride was removed by evaporation at reduced pressure.The residue was partitioned between CH₂ Cl₂ and cold water. The organicphase was separated, dried (MgSO₄) and concentrated by evaporation atreduced pressure. The resulting solid was added to 50 ml (0.22 mol) of a25 weight percent solution of sodium methoxide in methanol. Theresulting suspension was stirred at room temperature for 30 minutes,diluted with 50 ml of water and filtered. The solid collected was driedin vacuo to yield 1.41 g (41%) of the desired product as a light brownsolid, m.p. 112.5°-115° C. IR and ¹ H NMR spectra were consistent withthe assigned structure.

EXAMPLE 10 Preparation of2-benzylthio-7-methyl-1,2,4-triazolo[1,5-a]pyrimidine

A solution of 50 g (0.24 mol) of 3-amino-5-benzylthio-1,2,4-triazole in500 ml of glacial acetic acid was added dropwise over 3-4 hours to asolution of 34.0 g (0.25 mol) of acetylacetaldehyde dimethyl acetal in500 ml of glacial acetic acid heated at 100° C. After the addition wascomplete the reaction mixture was heated at reflux overnight, cooled toroom temperature and poured into an ice-water mixture. The solid whichseparated was collected by filtration and recrystallized from ethanol toyield 27 g (41%) of the desired product as a solid, m.p. 102°-104° C. IRand ¹ H NMR spectra were in agreement with the assigned structure.

Analysis:

Calculated for C₁₃ H₁₂ N₄ S: C, 60.94; H, 4.68; N, 21.85.

Found: C, 60.81; H, 4.68; N, 21.74.

EXAMPLE 11 Preparation of2-benzylthio-6-methyl-1,2,4-triazolo[1,5-a]pyrimidine

A suspension of 14.4 g (0.124 mol) of 3-amino-5-benzyl-1,2,4-triazoleand 30.0 g (0.124 mol) of 1,3-bis(dimethylamino)-2-methyltrimethiniumperchlorate in 500 ml of glacial acetic acid was heated at reflux for 63hours. The reaction mixture was subjected to the work-up described inExample 5 to yield 13.9 g (68%) of the desired product as a brown solid,m.p. 254°-256° C. IR and ¹ H NMR spectra were in agreement with theassigned structure.

Analysis:

Calculated for C₆ H₆ N₄ S: C, 43.35; H, 3.61; N, 33.72

Found: C, 42.71; H, 3.49; N, 33.26.

EXAMPLE 12 Preparation of2-benzylthio-6-chloro-5,7-dimethyl-1,2,4-triazolo[1,5-a]pyrimidine

To a suspension of 153 g (0.74 mol) 3-amino-5-benzylthio-1,2,4-triazolein 250 ml of glacial acetic acid was added 100 g (0.74 mol) of3-chloro-2,4-pentanedione in a dropwise manner. The reaction mixture washeated at reflux for 18 hours and cooled to room temperature. Thereaction mixture was poured over ice and the oil which separatedsolidified upon stirring. The solid was collected by filtration andrecrystallized from methanol to yield 116 g (79%) of the desired productas an off white solid, m.p. 164°-166° C. IR and ¹ H NMR spectra were inagreement with the assigned structure.

Analysis:

Calculated for C₁₄ H₁₃ ClN₄ S: C, 55.16; H, 4.30; N, 18.38.

Found: C, 55.11; H, 4.30; N, 18.34.

EXAMPLE 13 Preparation of2-benzylthio-6-ethoxy-1,2,4-triazolo[1,5-a]pyrimidine

This material was prepared in 28% yield from3-amino-5-benzylthio-1,2,4-triazole and1,3-bis(dimethylamino)-2-ethoxytrimethinium perchlorate following thegeneral procedure described in Example 5. The desired product wasisolated as a solid, m.p. 139°-140° C. IR and ¹ H NMR spectra were inagreement with the assigned structure.

Analysis:

Calculated for C₁₄ H₁₄ N₄ OS: C, 58.73; H, 4.89; N, 19.57.

Found: C, 58.68; H, 4.64; N, 19.58.

EXAMPLE 14 Preparation of2-benzylthio-2-benzylthio-5-isopropyl-1,2,4-triazolo[1,5-a]pyrimidine

This material was prepared in 96% yield from3-amino-5-benzylthio-1,2,4-triazole and 4-methyl-3-oxopentanal followingthe general procedure described in Example 7. The desired product wasisolated as a solid, m.p. 65°-66° C. IR and ¹ H NMR were in agreementwith the assigned structure.

Analysis:

Calculated for C₁₅ H₁₆ N₄ S: C, 63.36; H, 5.63; N, 19.71.

Found: C, 63.00; H, 5.62; N, 19.62.

EXAMPLE 15 Preparation of2-benzylthio-5,6-dimethyl-1,2,4-triazolo[1,5-a]pyrimidine

A solution of 5.0 g (24 mmol) of 3-amino-5-benzylthio-1,2,4-triazole and5.0 g (41 mmol) of the sodium salt of 2-methyl-3-oxobutanal in 200 ml ofglacial acetic acid was heated at reflux overnight. The solution wascooled to room temperature and the reaction mixture was concentrated byevaporation at reduced pressure. The residue was combined with ice andH₂ O to separate a tan solid. The solid was collected by filtration,dried and carefully recrystallized from ethyl acetate to yield 3.53 g(54%) of the desired product as a crystalline solid, m.p. 147°-149° C.IR and ¹ H NMR spectra were in agreement with the assigned structure.

Analysis:

Calculated for C₁₄ H₁₄ N₄ S: C, 62.10; H, 5.18; N, 20.72.

Found: C, 61.58; H, 5.18; N, 20.45.

EXAMPLE 16 Preparation of2-benzylthio-6-chloro-7-hydroxy-5-methyl-1,2,4-triazolo[1,5-a]pyrimidine

A solution of 16 g (77 mmol) of 3-amino-5-benzylthio-1,2,4-triazole and10.6 g (77 mmol) of ethyl 2-chloroacetoacetate in 150 ml of glacialacetic acid was heated at 100° C. for 17 hours. Upon cooling to roomtemperature the solid which separated was collected by filtration. Thefiltrate was diluted with ice water to separate an additional quantityof solid. The solids were combined and dried to yield 14.0 g (60% of thedesired product as a solid, m.p. 258°-260° C. IR and ¹ H NMR were inagreement with the assigned structure.

Analysis:

Calculated for C₁₃ H₁₁ ClN₄ OS: C, 50.89; H, 3.58; N, 18.27.

Found: C, 50.51; H, 3.36; N, 18.67.

EXAMPLE 17 Preparation of2-benzylthio-6,7-dichloro-5-methyl-1,2,4-triazolo[1,5-a]pyrimidine

This material was prepared in 68% yield from2-benzylthio-6-chloro-7-hydroxy-5-methyl-1,2,4-triazolo[1,5-a]pyrimidineand phosphorus oxychloride following the general procedure described inExample 20. The desired product was isolated as a solid, m.p. 103°-105°C. IR and ¹ H NMR spectra were in agreement with the assigned structure.

Analysis:

Calculated for C₁₃ H₁₀ Cl₂ N₄ S: C, 48.00; H, 3.07; N, 17.23.

Found: C, 47.40; H, 3.00; N, 17.43.

EXAMPLE 18 Preparation of2-benzylthio-6-chloro-5-methyl-1,2,4-triazolo[1,5-a]pyrimidine

This material was prepared by reduction of2-benzylthio-6,7-dichloro-5-methyl-1,2,4-triazolo[1,5-a]pyrimidine withzinc-copper couple following the general procedure described in Example21. The desired product was isolated in 88% yield as a solid, m.p.160°-161° C. IR and ¹ H NMR spectra were in agreement with the assignedstructure.

Analysis:

Calculated for C₁₃ H₁₁ ClN₄ S: C, 53.56; H, 3.56; N, 19.27.

Found: C, 53.30; H, 3.79; N, 19.28.

EXAMPLE 19 Preparation of2-benzylthio-5,7-dihydroxy-1,2,4-triazolo[1,5-a]pyrimidine

A solution of 125 g (0.58 mol) of a 25% solution of sodium methoxide inmethanol dissolved in 100 ml of absolute ethanol was treated with 66.3ml (0.29 mol) of dimethyl malonate followed by 60.0 g (0.20 mol) of3-amino-5-benzylthio-1,2,4-triazole. The resulting solution was heatedat reflux for 5 days. On cooling to room temperature the solid which hadseparated was collected by filtration, washed with cold ethanol anddissolved in 1000 ml of water. The resulting yellow solution wasacidified with concentrated HCl to precipitate a solid. The solid wascollected by filtration and dried to yield 70.1 g (82%) of the desiredproduct as a white solid, m.p. 199°-210° C. (decomposition). IR and ¹ HNMR spectra were in agreement with the assigned structure.

Analysis:

Calculated for C₁₂ H₁₀ N₄ O₂ S.H₂ O: C, 49.30; H, 4.14, N, 19.16.

Found: C, 48.70; H, 3.89; N, 18.83.

EXAMPLE 20 Preparation of2-benzylthio-5,7-dichloro-1,2,4-triazolo[1,5-a]pyrimidine

A suspension of 70.0 g (0.24 mol) of2-benzylthio-5,7-dihydroxy-1,2,4-triazolo[1,5-a]pyrimidine and 67.0 ml(0.72 mol) of phosphorous oxychloride in 600 ml of acetonitrile washeated at reflux for 3 hours. The resulting orange solution was stirredat room temperature overnight (17 hours). The solution was filtered andthe filtrate was concentrated by evaportion at reduced pressure. Theresidue was partitioned between cold water and methylene chloride, andthe organic phase was separated and dried (MgSO₄). The organic phase wasconcentrated to induce crystallization. The desired product wascollected by filtration to yield 98.0 g (81%) of solid, m.p. 97°-100° C.IR and ¹ H NMR spectra were in agreement with the assigned structure.

Analysis:

Calculated for C₁₂ H₈ Cl₂ N₄ S: C, 46.32; H, 2.59; N, 18.00.

Found: C, 46.43; H, 2.57; N, 18.08.

EXAMPLE 21 Preparation of2-benzylthio-5-chloro-1,2,4-triazolo[1,5-a]pyrimidine

A zinc-copper couple was prepared following the precedure of Bradley (J.Org. Chem. 31, 626 (1966)) by stirring 1.0 g of copper sulfate in 20 mlof water with 15.0 g of zinc dust for 2 hours. The couple was collectedby filtration, washed with acetone and dried overnight under vacuum at100° C. To a solution of 33.0 g (106 mmol) of2-benzylthio-5,7-dichloro-1,2,4-triazolo[1,5-a]pyrimidine in 12.5 ml(213 mmol) of acetic acid, 50 ml of methanol and 300 ml oftetrahydrofuran was added 20.5 g of Zn-Cu couple. The mixture wasstirred overnight at 22°-23° C. When the reaction was complete (TLCanalysis) the reaction mixture was filtered through celite and thefiltrate was concentrated by evaporation at reduced pressure. Theresidue was triturated with hexane to separate a solid. The solid wascollected by filtration to yield the desired product as 26.5 g (92%) oforange solid, m.p. 125°-127° C. IR and ¹ H NMR spectra were in agreementwith the assigned structure.

Analysis:

Calculated for C₁₂ H₉ ClN₄ S: C, 52.08; H, 3.25; N, 20.25.

Found: C, 51.76; H, 3.00; N, 20.27.

EXAMPLE 22 Preparation of2-benzylthio-5-methoxy-1,2,4-triazolo[1,5-a]pyrimidine

A mixture of 6.0 g (22 mmol) of2-benzylthio-5-chloro-1,2,4-triazolo[1,5-a]pyrimidine in 25 ml ofmethanol was treated with 5.0 g (23.8 mmol) of a 25% solution of sodiummethoxide in methanol. After stirring for 1.5 hours the reaction mixturewas diluted with 100 ml of water and neutralized with 3N HCL (aq). Thesolid which separated was collected by filtration, washed with water anddried to afford 5.0 g (84%) of the desired product as a white solid,m.p. 126°-128° C. IR and ¹ H NMR spectra were in agreement with theassigned structure.

Analysis:

Calculated for C₁₃ H₁₂ N₄ OS: C, 57.34; H, 4.41; N, 20.58.

Found: C, 57.21; H, 4.42; N, 20.13.

EXAMPLE 23 Preparation of2-benzylthio-5-(2,2,2-trifluoroethoxy)-1,2,4-triazolo[1,5-a]pyrimidine

A solution of sodium 2,2,2-trifluoroethoxide in tetrahydrofuran wasprepared by the addition of 1.1 g (48 mg-atom) of sodium metal to asolution of 3.5 ml (48 mmol) of 2,2,2-trifluoroethanol in 100 ml oftetrahydrofuran. To this solution was added 7.0 g (25 mmol) of2-benzylthio-5-chloro-1,2,4-triazolo[1,5-a]pyrimidine, and the reactionmixture was stirred for 30 minutes and concentrated by evaporation atreduced pressure to approximately one quarter of the original volume.Pentane (200 ml) was added to induce crystallization. The solid whichseparated was collected by filtration to yield 6.42 g (75%) of thedesired product as a light yellow solid, m.p. 114°-118° C. IR and ¹ HNMR spectra were in agreement with the assigned structure.

Analysis:

Calculated for C₁₄ H₁₁ F₃ N₄ OS: C, 49.40; H, 3.23; N, 16.46.

Found: C, 49.63; H, 3.09; N, 16.70.

EXAMPLE 24 Preparation of2-benzylthio-5-ethoxy-1,2,4-triazolo[1,5-a]pyrimidine

This material was prepared by heating 2benzylthio-5-(2,2,2-trifluoroethoxy)-1,2,4-triazolo[1,5-a]pyrimidine inboiling ethanol. The hot mixture was filtered and the filtrate wasconcentrated. The crude product was recrystallized from isopropanol toyield the desired product as a solid, m.p. 115°-117° C. IR and ¹ H NMRspectra were in agreement with the assigned structure.

Analysis:

Calculated for C₁₄ H₁₄ N₄ OS: C, 58.73; H, 4.89; N, 19.31; S, 11.20.

Found: C, 57.90; H, 4.69; N, 19.30; S, 10.79.

EXAMPLE 25 Preparation of2-benzylthio-5,7-dihydroxy-6-methyl-1,2,4-triazolo[1,5-a]pyrimidine

This material was prepared in 80% yield from3-amino-5-benzylthio-1,2,4-triazole and dimethyl 2-methyl malonatefollowing the general procedure described in Example 19. The product wasisolated as a solid, m.p. 260°-272° C. (decomposition). IR and ¹ H NMRspectra were in agreement with the assigned structure.

Analysis:

Calculated for C₁₃ H₁₂ N₄ O₂ S: C, 54.15; H, 4.16; N, 19.44.

Found: C, 53.48; H, 4.07; N, 19.53.

EXAMPLE 26 Preparation of2-benzylthio-5,7-dichloro-6-methyl-1,2,4-triazolo[1,5-a]pyrimidine

This material was prepared in 97% yield from the reaction of2-benzylthio-5,7-dihydroxy-6-methyl-1,2,4-triazolo[1,5-a]pyrimidine andphosphorous oxychloride following the general procedure described inExample 20. The product was isolated as a solid, m.p. 121°-123° C. IRand ¹ H NMR spectra were in agreement with the assigned structure.

Analysis:

Calculated for C₁₃ H₁₀ Cl₂ N₄ S: C, 48.01; H, 3.08; N, 17.23.

Found: C, 47.65; H, 3.11; N, 17.70.

EXAMPLE 27 Preparation of2-benzylthio-5-chloro-6-methyl-1,2,4-triazolo[1,5-a]pyrimidine

This material was prepared in 32% yield by reduction of2-benzylthio-5,7-dichloro-6-methyl-1,2,4-trizolo[1,5-a]pyrimidine withzinc-copper couple following the general procedure described in Example21. The desired product was isolated as a solid, m.p. 179°-181° C. IRand ¹ H NMR spectra were in agreement with the assigned structure.

Analysis:

Calculated for C₁₃ H₁₁ ClN₄ S: C, 53.70; H, 3.79; N, 19.28.

Found: C, 53.33; H, 3.73; N, 19.53.

EXAMPLE 28 Preparation of2-benzylthio-5-methoxy-6-methyl-1,2,4-triazolo[1,5-a]pyrimidine

This material was prepared in 64% yield by reaction of2-benzylthio-5-chloro-6-methyl-1,2,4-triazolo[1,5-a]pyrimidine withsodium methoxide following the general procedure described in Example22. The desired product was isolated as a solid, m.p. 145°-146° C. IRand ¹ H NMR spectra were in agreement with the assigned structure.

Analysis:

Calculated for C₁₄ H₁₄ N₄ OS: C, 58.73; H, 4.89; N, 19.58.

Found: C, 58.34; H, 4.84; N, 19.67.

EXAMPLE 29 Preparation of2-benzylthio-6-ethoxycarbonyl-7-methyl-1,2,4-triazolo[1,5-a]pyrimidine

A solution of 15 g (73 mmol) of 3-amino-5-benzylthio-1,2,4-triazole and15.0 g (80.0 mmol) of ethyl ethoxymethyleneacetoacetate in 250 ml ofglacial acetic acid was heated at reflux for 60 hours. After cooling thevolume of the reaction was reduced to approximately one quarter of theoriginal volume by evaporation at reduced pressure. The resultingresidue was poured into water, and the solid which separated wascollected by filtration, washed with water and dried to yield 7.88 g(33%) of the desired product as a solid, m.p. 98°-99° C. IR and ¹ H NMRspectra were in agreement with the assigned structure.

Analysis:

Calculated for C₁₆ H₁₆ N₄ O₂ S: C, 58.52; H, 4.87; N, 17.07.

Found: C, 58.51; H, 4.89; N, 17.03.

EXAMPLE 30 Preparation of2-benzylthio-6-(4-nitrophenyl)-1,2,4-triazolo[1,5-a]pyrimidine

This material was prepared from 3-amino-5-benzylthio-1,2,4-triazole and1,3-bis(dimethylamino)-2-(4-nitrophenyl)-trimethinium percholatefollowing the general procedure described in Example 5. The desiredproduct was isolated as a solid, m.p. 195°-199° C. IR and ¹ H NMRspectra were in agreement with the assigned structure.

EXAMPLE 31 Preparation of2-benzylthio-5,6-cyclopentano-7-hydroxy-1,2,4-triazolo[1,5-a]pyrimidine

A solution of 20.6 g (100 mmol) of 3-amino-5-benzylthio-1,2,4-triazoleand 15 ml (16 g, 0.10 mol) of 2-carboethoxycyclopentanone in 110 ml ofglacial acetic acid was heated at reflux for 23 hours. After cooling toroom temperature the solid which separated from the reaction mixture wascollected by filtration, washed with acetic acid and dried in vacuo toyield 22.4 g (75%) of the desired product as a colorless crystallinesolid, m.p. 241°-243° C. IR and ¹ H NMR spectra were in agreement withthe assigned structure.

Analysis:

Calculated for C₁₅ H₁₄ N₄ OS: C, 60.38; H, 4.73; N, 18.78; S, 10.75.

Found: C, 60.10; H, 4.66; N, 18.91; S, 10.72.

EXAMPLE 32 Preparation of2-benzylthio-7-chloro-5,6-cyclopentano-1,2,4-triazolo[1,5-a]pyrimidine

A solution of 5.97 g (20.0 mmol) of2-benzylthio-5,6-cyclopentano-7-hydroxy-1,2,4-triazolo[1,5-a]pyrimidinein 250 ml of phosphorus oxychloride was heated at reflux for 50 minutes.After cooling to room temperature the excess phosphorous oxychloride wasremoved by distillation at aspirator pressure. The residue waspartitioned between ice cold water and methylene chloride. The organicphase was dried (Na₂ SO₄) and evaporated at reduced pressure. Theresidue was chromatographed on silica gel eluting with EtOAc hexane(1:1, v/v) to yield 3.72 g (59%) of the desired product as a yellowsolid, m.p. 119°-120° C. IR and ¹ H NMR spectra were in agreement withthe assigned structure.

Analysis:

Calculated for C₁₅ H₁₃ ClN₄ S: C, 56.87; H, 4.14; N, 17.68; Cl, 11.19;S, 10.12.

Found: C, 56.91; H, 4.06; N, 17.83; Cl, 10.68; S; 9.65.

EXAMPLE 33 Preparation of2-benzylthio-5,6-cyclopentano-7-methyl-1,2,4-triazolo[1,5-a]pyrimidine

A solution of 2.47 g (7.80 mmol) of2-benzylthio-7-chloro-5,6-cyclopentano-1,2,4-triazolo[1,5-a]pyrimidinein 40 ml of dry tetrahydrofuran was cooled to 5° C. and 5.9 ml (17 mmol)of 2.9M methyl magnesium bromide in ether was added over 5 minutes.After the addition was complete the reaction mixture was warmed to roomtemperature and stirred overnight (17 hours). The reaction was quenchedby addition of 10 ml of saturated aqueous ammonium chloride. The organicphase was separated, dried (Na₂ SO₄) and evaporated at reduced pressure.The red oil residue was chromatographed on silica gel (HPLC) elutingwith EtOAc-hexane (1:1, v/v) to yield 1.12 g (48%) of the desiredproduct as a pale red solid, m.p. 109°-111° C. IR and ¹ H NMR spectrawere in agreement with the assigned structure.

Analysis:

Calculated for C₁₆ H₁₆ N₄ S: C, 64.84; H, 5.44; N, 18.90; S, 10.82.

Found: C, 64.99; H, 5.41; N, 18.16; S, 10.42.

EXAMPLE 34 Preparation of2-benzylthio-5,7-bis-(trifluoromethyl)-1,2,4-triazolo[1,5-a]pyrimidine

A solution of 20.8 g (0.100 mol) of1,1,1,5,5,5-hexafluoro-2,4-pentanedione and 20.6 g (0.100 mol) of3-amino-5-benzylthio-1,2,4-triazole in 150 ml of glacial acetic acid washeated at reflux for 14 hours. The solution was cooled to roomtemperature and poured over ice. The solid which separated was collectedby filtration, washed with water and dried in vacuo to yield 35.5 g(94%) of the desired product as a pale yellow solid, m.p. 78.5°-80.5° C.IR, ¹ H NMR and ¹⁹ F NMR spectra were in agreement with the assignedstructure.

Analysis:

Calculated for C₁₄ H₈ F₆ N₄ S: C, 44.45; H, 2.13; N, 14.81; S, 8.48.

Found: C, 44.53; H, 2.15; N, 14.97; S, 8.39.

EXAMPLE 35 Preparation of2-benzylthio-5-methyl-7-trifluoromethyl-1,2,4-triazolo[1,5-a]pyrimidine

This material was prepared in 84% yield from3-amino-5-benzylthio-1,2,4-triazole and 1,1,1-trifluoro-2,4-pentanedionefollowing the general procedure described in Example 34. The product waspurified by recrystallization from benzene-hexane to yield a tan solid,m.p. 83.5°-84.5° C. IR, ¹ H NMR and ¹⁹ F NMR spectra were in agreementwith the assigned structure.

Analysis:

Calculated for C₁₄ H₁₁ F₃ N₄ S: C, 51.85; H, 3.42; N, 17.27; S, 9.89.

Found: C, 51.73; H, 3.44; N, 18.01; S, 10.08.

EXAMPLE 36 Preparation of2-benzylthio-5,7-diphenyl-1,2,4-triazolo[1,5-a]pyrimidine

A solution of 8.40 g (37.5 mmol) of dibenzoylmethane and 7.73 g (37.5mmol) of 3-amino-5-benzylthio-1,2,4-triazole in 50 ml of glacial aceticacid was heated at reflux for 24 hours. Upon cooling to room temperaturethe solid which separated was collected by filtration and dried. Theproduct was chromatographed on silica gel (HPLC) eluting withEtOAc-hexane (3:7, v/v) to afford 5.08 g (34%) of the desired product asa colorless solid, m.p. 122.5°-123.5° C. IR and ¹ H NMR spectra were inagreement with the assigned structure.

Analysis:

Calculated for C₂₄ H₁₈ N₄ S: C, 73.07; H, 4.60; N, 14.20; S, 8.13.

Found: C, 73.48; H, 4.54; N, 14.17; S, 7.97.

EXAMPLE 37 Preparation of2-benzylthio-5-methyl-7-phenyl-1,2,4-triazolo[1,5-a]pyrimidine and2-benzylthio-7-methyl-5-phenyl-1,2,4-triazolo[1,5-a]pyrimidine

A solution of 20.6 g (100 mmol) of 3-amino-5-benzylthio-1,2,4-triazoleand 16.2 g (100 mmol) of benzoyl acetone in 100 ml of glacial aceticacid was heated at reflux for 14 hours. The solvent was removed byevaporation at reduced pressure and the residue was chromatographed onsilica gel (HPLC) eluting with EtOAc-hexane (3:7, v/v) to afford 4.81 g(14% of 2-benzylthio-7-methyl-5-phenyl-1,2,4-triazolo[1,5-a]pyrimidineas a pale yellow wolid, m.p. 154°-155° C. IR and ¹ H NMR spectra were inagreement with the assigned structure.

Analysis:

Calculated for C₁₉ H₁₆ N₄ S: C, 68.65; H, 4.85; N, 16.85; S, 9.65.

Found: C, 68.76; H, 4.82; N, 16.98; S, 9.93.

Further elution afforded 22.8 g (69%) of2-benzylthio-5-methyl-7-phenyl-1,2,4-triazolo[1,5-a]pyrimidine as a paleyellow solid, m.p. 110°-111° C. IR and ¹ H NMR spectra were in agreementwith the assigned structure.

Analysis:

Calculated for C₁₉ H₁₆ N₄ S: C, 68.65; H, 4.85; N, 16.85; S, 9.65.

Found: C, 68.52; H, 4.75; N, 16.93; S, 9.61.

EXAMPLE 38 Preparation of5,7-dimethyl-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonyl chloride

Chlorine was bubbled into a suspension of 99.0 g (0.366 mol) of2-benzylthio-5,7-dimethyl-1,2,4-triazolo[1,5-a]pyrimidine in 700 ml ofHOAc-H₂ O (1:1, v/v) cooled to -1° C. During the course of the additionthe temperature of the reaction mixture was maintained below 5° C. After2.5 hours the chlorine addition was ceased and the reaction mixture wasfiltered to collect a tan solid. The filtrate was diluted with H₂ O toseparate an additional quantity of solid which was collected byfiltration. The combined solid products were dried in vacuo to yield70.4 g (78%) of crude sulfonyl chloride III (X=Z=Me, Y=H) as a tansolid. IR and ¹ HNMR spectra confirmed the structure.

Recrystallization from EtOAc produced an analytical sample as anoff-white solid, m.p. 128.5°-130.5° C.

Analysis:

Calculated for C₇ H₇ ClN₄ O₂ S: C, 34.09; H, 2.86; N, 20.73; S, 13.00.

Found: C, 34.34; H, 2.80; N, 22.64; S, 12.85.

EXAMPLE 39 Preparation of6,7-cyclopentano-5-methyl-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonylchloride

Chlorine gas was bubbled into a suspension of 4.45 g (15.0 mmol) of2-benzylthio-6,7-cyclopentano-5-methyl-1,2,4-triazolo[1,5-a]pyrimidinein 30 ml of HOAC-H₂ O (1:1, v/v) cooled to -4° C. After 30 minutes theaddition was stopped and the reaction was stirred for 30 minutesmaintaining the temperture below 5° C. The reaction mixture was filteredand the collected solid was dried under vacuum to yield 3.46 g (85percent) of the desired sulfonyl chloride as a cream colored solid whichwas used directly without further purification: IR (CHCl₃) 1627, 1551,1398 and 1170 cm⁻¹ ; ¹ H NMR (CDCl₃) δ3.50 (2H, broad t), 3.18 (2H,broad t) and 2.2-2.8 (5H, broad t), 3.18 (2H, broad t) and 2.2-2.8 (5H,m including s at 2.68).

EXAMPLE 40 Preparation of5,6,7-trimethyl-1,2,4-triazolo[1,5a]pyrimidine-2-sulfonyl chloride

Chlorine was bubbled into a suspension of 28.4 g (0.100 mol) of2-benzylthio-5,6,7-trimethyl-1,2,4-triazolo[1,5-a]pyrimidine in 200 mlof glacial acetic acid-H₂ O (1:1, v/v) and cooled to -5° C. The chlorineaddition continued over 35 minutes and the temperature of the reactionmixture never exceeded 5° C. After the addition was complete, thereaction mixture was stirred for 5 minutes and filtered. The solidcollected was washed twice with H₂ O and dried in vacuo to yield 24.3 g(93%) of the crude sulfonyl chloride as a pale yellow solid. The IR and¹ H NMR were consistent with the assigned structure. The crude solfonylchloride was used in subsequent transformations without furtherpurification.

EXAMPLE 41 Preparation of6-chloro-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonyl chloride

A suspension of 3.75 g (13.5 mmol) of2-benzylthio-6-chloro-1,2,4-triazolo[1,5-a]pyrimidine in 40 ml ofAcOH-H₂ O (1:1, v/v) was cooled to -10° C. and chlorine gas was bubbledinto the reaction mixture for 10 minutes. After the addition wascomplete, the reaction mixture was stirred for 10 minutes and dilutedwith 25 ml of H₂ O. The mixture was filtered and the filtrate wasextracted with CH₂ Cl₂. The organic phase was evaporated at reducedpressure to afford 2.14 g of the crude sulfonyl chloride as a liquid. IRand ¹ H NMR spectra were in agreement with the assigned structure.

EXAMPLE 42 Preparation of 1,2,4-triazolo[1,5-a]-pyrimidine-2-sulfonylchloride

A suspension of 8.0 g (33 mmol) of2-benzylthio-1,2,4-triazolo[1,5-a]pyrimidine in 60 ml of HOAc-H₂ O (1:1,v/v) was cooled below 0° C. and chlorine gas was bubbled into thereaction mixture for 15 minutes. The temperature of the reaction mixturewas maintained below 10° C. during the course of the addition. After theaddition was complete, the reaction mixture was stirred for 15 minutes,diluted with H₂ O and extracted with CH₂ Cl₂. The organic phase wasdried (MgSO₄) and evaporated at reduced pressure to yield 5.74 g of thedesired crude product as a brown oil, IR and ¹ H NMR were in agreementwith the assigned structure.

Recrystallization from EtOAc gave an analytical sample, m.p. 105°-109°C.

Analysis:

Calculated for C₅ H₃ ClN₄ O₂ S: C, 27.45; H, 1.32; N, 25.62.

Found: C, 28.91; H, 1.52; N, 25.79.

EXAMPLE 43 Preparation of5-methyl-1,2,4-triazolo-[1,5-a]pyrimidine-2-sulfonyl chloride

A suspension of 2.77 g (10.8 mmol) of2-benzylthio-5-methyl-1,2,4-triazolo[1,5-a]pyrimidine in 40 ml ofAcOH-H₂ O (1:1, v,v) was cooled to -10° C. and chlorine gas was bubbledinto the solution for 10 minutes. After the addition was complete, thereaction mixture was stirred for 5 minutes, diluted with H₂ O (25 ml)and filtered. The solid collected was dried in vacuo to yield 1.17 g ofthe desired sulfonyl chloride. IR and ¹ H NMR were in agreement with theassigned structure.

An addition quantity of the product contaminated with by-productscontaining benzyl residues was obtained byextraction of the filtratewith CH₂ Cl₂ and evaporation of the organic phase at reduced pressure.

EXAMPLE 44 Preparation of5-methoxy-7-methyl-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonyl chloride

A suspension of 1.41 g (4.93 mmol) of2-benzylthio-5-methoxy-7-methyl-1,2,4-triazolo[1,5-a]pyrimidine in 40 mlof AcOH-H₂ O (1:1, v/v) was cooled to -20° C., and chlorine gas wasbubbled into the reaction mixture for 5 minutes. After the addition wascomplete, the reaction mixture was stirred for 10 minutes, diluted withH₂ O (20 ml) and filtered. The solid collected was dried in vacuo toyield 0.63 g of the desired crude sulfonyl chloride as a colorlesssolid. IR and ¹ H NMR were in agreement with the assigned structure.

EXAMPLE 45 Preparation of7-methyl-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonyl chloride

A suspension of 3.52 g (13.7 mmol) of2-benzylthio-5-methyl-1,2,4-triazolo[1,5-a]pyrimidine in 40 ml ofAcOH-H₂ O (1:1, v/v) was cooled to -10° C., and chlorine gas was bubbledinto the reaction mixture for 10 minutes. After the addition wascomplete, the reaction mixture was stirred for 10 minutes, diluted withH₂ O and filtered. The solid collected was dried in vacuo to yield 0.46g of the desired sulfonyl chloride as a tan solid. IR and ¹ H NMRspectra were in agreement with the assigned structure.

An additional quantity (2.2 g) of crude sulfonyl chloride contaminatedwith by-products containing benzyl residues was obtained by extractionof the filtrate with CH₂ Cl₂ and evaporation at reduced pressure.

EXAMPLE 46 Preparation of6-methyl-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonyl chloride

A suspension of 10.0 (60 mmol) of2-benzylthio-6-methyl-1,2,4-triazolo[1,5-a]pyrimidine in 260 ml ofmethylene chloride, 100 ml of water and 17 ml of concentrated HCl wascooled to -5° C. and treated with 284 ml (197 mmol) of 5.25% aqueoussodium hypochlorite (commercial bleach) by dropwise addition. After theaddition was complete the reaction mixture was stirred for 20 minutes at0° C. and filtered. The organic layer was separated and the aqueouslayer was extracted twice with methylene chloride. The combined organicphases were dried (MgSO₄) and evaporated at reduced pressure to yield7.0 g (50%) of the desired product as a solid, mp 106°-108° C. IR and ¹H NMR spectra were in agreement with the assigned structure.

Analysis:

Calculated for C₆ H₅ ClN₄ O₂ S: C, 30.96; H, 2.15; N, 24.08

Found: C, 31.00; H, 2.23; N, 23.91

EXAMPLE 47 Preparation of6-chloro-5,7-dimethyl-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonylchloride

This material was prepared in 50% yield from2-benzylthio-6-chloro-5,7-dimethyl-1,2,4-triazolo [1,5-a]pyrimidinefollowing the general procedure described in Examples 38-45. The productwas isolated as a pale yellow solid, mp 131°-133° C. IR and ¹ H NMRspectra were in agreement with the assigned structure.

EXAMPLE 48 Preparation of6-ethoxy-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonyl chloride

This material was prepared in 82% yield from2-benzylthio-6-ethoxy-1,2,4-triazolo[1,5-a]pyrimidine following thegeneral procedure described in Examples 38-45. The product was isolatedas a solid, mp 134°-137° C. IR and ¹ H NMR spectra were in agreementwith the assigned structure.

Analysis:

Calculated for C₇ H₇ ClN₄ O₃ S: C, 31.96; H, 2.66; n, 21.31.

Found: C, 32.64; H, 2.36; N, 21.30.

EXAMPLE 49 Preparation of5-isopropyl-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonyl chloride

This material was prepared in 56% yield from2-benzylthio-5-isopropyl-1,2,4-triazolo[1,5-a]pyrimidine following thegeneral procedure described in Example 46. The product was isolated as asolid, mp 60°-62° C. IR and ¹ H NMR spectra were in agreement with theassigned structure.

Analysis:

Calculated for C₈ H₉ ClN⁴ O₂ S: C, 36.85; H, 3.45; N, 21.49.

Found: C, 37.02; H, 3.49; N, 21.71.

EXAMPLE 50 Preparation of5,6-dimethyl-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonyl chloride

This material was prepared in 80% yield from2-benzylthio-5,6-dimethyl-1,2,4-triazolo[1,5-a]pyrimidine following thegeneral procedure described in Example 46. The product was isolated as asolid, mp 116°-120° C. IR and ¹ H NMR spectra were in agreement with theassigned structure.

Exact mass calculated for C₇ H₇ ClN₄ O₂ S: 245.9984

Found: 245.9981

EXAMPLE 51 Preparation of6-chloro-5-methyl-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonyl chloride

This material was prepared in 60% yield from2-benzylthio-6-chloro-5-methyl-1,2,4-triazolo[1,5-a]pyrimidine followingthe general procedure described in Examples 38-45. The product wasisolated as a solid, mp 99°-101° C. IR and ¹ H NMR spectra were inagreement with the assigned structure.

EXAMPLE 52 Preparation of5-methoxy-1,2,4-triazolo-[1,5-a]pyrimidine-2-sulfonyl chloride

This material was prepared in 57% yield from2-benzylthio-5-methoxy-1,2,4-triazolo[1,5-a]pyrimidine following thegeneral procedure described in Examples 38-45. The product was isolatedas a solid, mp 110°-112° C. IR and ¹ H NMR spectra were in agreementwith the assigned structure.

Analysis:

Calculated for C₆ H₅ ClN₄ O₃ S: C, 28.97; H, 2.01; N, 22.53.

Found: C, 29.90; H, 2.23; N, 22.76.

EXAMPLE 53 Preparation of5-(2,2,2-trifluoroethoxy)1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonylchloride

This material was prepared in 74% yield from2-benzylthio-5-(2,2,2-trifluoroethoxy)-1,2,4-triazolo[1,5-a]pyrimidinefollowing the general procedure described in Examples 38-45. The productwas isolated as a solid, mp 91°-96° C. IR and ¹ H NMR spectra were inagreement with the assigned structure.

Exact mass calculated for C₇ H₄ ClF₃ N₄ O₃ S: 315.9655

Found: 315.9650

EXAMPLE 54 Preparation of5-ethoxy-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonyl chloride

This material was prepared in 74% yield from2-benzylthio-5-ethoxy-1,2,4-triazolo[1,5-a]pyrimidine following thegeneral procedure described in Examples 38-45. The product was isolatedas a solid, mp 91°-96° C. IR and ¹ H NMR spectra were in agreement withthe assigned structure.

EXAMPLE 55 Preparation of5-methoxy-6-methyl-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonyl chloride

This material was prepared in 80% yield from2-benzylthio-5-methoxy-6-methyl-1,2,4-triazolo[1,5-a]-pyrimidinefollowing the general procedure outlined in Examples 38-45. The producewas isolated as a solid, mp 154°-157° C. IR and ¹ H NMR spectra were inagreement with the assigned structure.

Analysis:

Calculated for C₇ H₇ ClN₄ O₃ S: C, 32.00; H, 2.67; N, 21.33.

Found: C, 32.35; H, 2.61; N, 21.45.

EXAMPLE 56 Preparation of6-ethoxycarbonyl-7-methyl-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonylchloride

This material was prepared in 82% yield from2-benzylthio-6-ethoxycarbonyl-7-methyl-1,2,4-triazolo-[1,5-a]pyrimidinefollowing the general procedure described in Example 46. The product wasisolated as a solid, mp 65°-69° C. IR and ¹ H NMR spectra were inagreement with the assigned structure.

Analysis:

Calculated for C₉ H₉ ClN₄ O₄ S: C, 35.47; H, 2.95; N, 18.39

Found: C, 36.04; H, 3.02; N, 18.27

EXAMPLE 57 Preparation of6-(4-nitrophenyl)-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonyl chloride

This material was prepared in 71% yield from2-benzylthio-6-(4-nitrophenyl)-1,2,4-triazolo[1,5-a]-pyrimidinefollowing the general procedure described in Examples 38-45. The productwas isolated as a solid, mp 159°-167° C. IR and ¹ H NMR spectra were inagreement with the assigned structure.

EXAMPLE 58 Preparation of5,7-dimethyl-N-(2-chlorophenyl)-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonamide

To a solution of 0.74 ml (0.90 g, 7.0 mmol) of o-chloroaniline in 10 mlof dry pyridine was added 1.89 g (7.66 mmol) of the sulfonyl chlorideprepared in Example 38. The resulting dark solution was stirred atambient temperature for 18 hours and evaporated to dryness. The residuewas treated with 15 ml of 1N NaOH and charcoal and stirred for 15minutes. The mixture was filtered through celite and the filrate wasacidified with 3N HCl to precipitate the product. Filtration and dryingin vacuo gave the desired product (2.01 g, 85%) as a light brown solid,m.p. 188°-189.5° C. IR and ¹ H NMR spectra were in agreement with thedesired compound of formula I (Ar═o-chlorophenyl, X═Z═Me, Y═H).

Analysis:

Calculated for C₁₃ H₁₂ ClN₅ O₂ S: C, 46.23; H, 3.58; N, 20.73; Cl,10.50; S, 9.49.

Found: C, 46.09; H, 3.48; N, 20.89; Cl, 10.34; S, 9.37.

EXAMPLE 59 Preparation of methylN-(5,7-dimethyl-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonyl)anthranilate

To a solution of 0.91 ml (1.1 g, 7.0 mmol) of methyl anthranilate in 10ml of dry pyridine was added 1.89 g (7.66 mmol) of the sulfonyl chlorideprepared in Example 38. The resulting dark solution was stirred at roomtemperature for 18 hours and evaporated to dryness. The residue wastreated with 15 ml of 1N NaOH and charcoal and stirred for 15 minutes.The mixture was filtered through celite, and the filtrate was acidifiedwith 3N HCl to precipitate the product. The product was collected byfiltration and dried in vacuo to yield 2.27 g (90%) of the desiredproduct of Formula I (X═Z═Me, Y═H, Ar═o-carbomethoxyphenyl) as a creamcolored solid, m.p. 169.5°-170.5° C. IR and ¹ H NMR spectra confirmedthe structure of the product.

Analysis:

Calculated for C₁₅ H₁₅ N₅ O₄ S: C, 49.86; H, 4.18; N, 19.38; S, 8.87.

Found: C, 49.68; H, 4.13; N, 19.35; S, 8.69.

EXAMPLE 60 Preparation of5,7-dimethyl-N-(2,6-dimethylphenyl)-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonamide

A solution of 2.2 g (8.9 mmol) of5,7-dimethyl-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonyl chloride, 1.01ml (8.4 mmol) of 2,6-dimethylaniline, 0.7 ml (8.4 mmol) of dry pyridineand 4 mg of DMAP in 20 ml of CH₂ Cl₂ was stirred at room temperature for17 hours. The solvent was removed by evaporation and the residue wastaken up in 0.5M NaOH. The solution was extracted with diethyl ether andthe aqueous phase was acidified with 3N HCl to precipitate a solid. Thesolid was collected by filtration and dried in vacuo to yield 2.72 g (97percent) of the desired product as a white solid, m.p. 263°-266° C.(decomp.): ¹ H NMR (DMSO-d₆)δ10.4 (1H, broad S), 7.55 (1H, s), 7.2 (3H,s), 2.7 and 2.8 (3H each, s) and 2.1 (6H, s); IR (KBr) 3100, 2980-2780,1628, 1540 and 1355 cm⁻¹.

Analysis:

Calculated for C₁₅ H₁₇ N₅ O₂ S: C, 54.31; H, 5.23; N, 21.23.

Found: C, 53.59; H, 5.07; N, 20.65.

EXAMPLE 61 Preparation of6,7-cyclopentano-5-methyl-N-(2,6-dichlorophenyl)-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonamide

A solution of 3.31 g (12.1 mmol) of crude6,7-cyclopentano-5-methyl-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonylchloride and 1.87 g (11.6 mmol) of 2,6-dichloroaniline in 15 ml of drypyridine was stirred at 45°-50° C. for 23 hours. The majority of thepyridine was removed by evaporation at reduced pressure, and the residuewas treated with 25 ml of 1N NaOH and ice. After stirring for 15minutes, the mixture was filtered and the filtrate was acidified with 3NHCl to precipitate a light brown solid. The solid was taken up in 0.5NNaOh and filtered. The filtrate was acidified with 3N HCl to precipitatea solid. The solid was collected by filtration and dried in vacuo toyield 1.19 g (26 percent) of the desired sulfonamide as a light brownsolid, m.p. 264°-266° C.: ¹ H NMR (DMSO-d₆) δ10.83 (1H, broad s),7.1-7.6 (3H, m) and 2.0-3.6 (9H, m including s at 2.57); IR (KBr) 3410,1620, 1549, 1442, 1399, 1358 and 1167⁻¹.

Analysis:

Calculated for C₁₅ H₁₃ Cl₂ N₅ O₂ S: C, 45.24; H, 3.29; N, 17.58.

Found: C, 45.47; H, 3.18; N, 17.41.

EXAMPLE 62 Preparation of5,7-dmethyl-N-(2,4,6-trichlorophenyl)-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonamide

A solution (10.7 ml, 17.1 mmol) of 1.60 M N-butyllithium in hexane wasadded to a solution of 3.20 g (16.3 mmol) of 2,4,6-trichloroaniline in20 ml of dry THF cooled to -78° C. The resultant solution was thenallowed to warm to room temperature. This solution was added to asolution of 2.00 g (8.11 mmol) of5,7-dimethyl-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonyl chloride in 30ml of dry THF cooled to -10° C. The temperature of the reaction mixturewas maintained between -13° C. and -l9° C. during to course of theaddition. After the addition was complete, the reaction mixture wasstirred for 30 minutes and warmed to room temperature. After 1 hour atroom temperature, THF was removed from the reaction mixture byevaporation. The residue was triturated with H₂ O and filtered. Thefiltrate was treated with charcoal and filtered through celite. Thefiltrate was washed with Et.sub. 2 O, and the aqueous phase wasseparated and acidified with 3N HCl to precipitate a solid. The solidwas collected by filtration, washed with water and drid in vacuo toyield 0.70 g (21%) of the desired product as a tan solid, m.p. >200° C.(decomp.) ¹ H NMR and IR spectra were consistent with the assignedstructure.

Analysis:

Calculated for C₁₃ H₁₀ N₅ O₂ S: C, 38.40; H, 2.48; N, 17.22.

Found: C, 38.36; H, 2.48; N, 17.14.

EXAMPLE 63 Preparation of6-chloro-N-(2,6-difluorophenyl)-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonamide

The starting 2,6-difluoroaniline (1.7 g, 13 mmol) was dissolved in 3.5ml of pyridine and 3.5 g (14 mmol) of6-chloro-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonyl chloride was added.After an exothermic reaction subsided the reaction mixture was heated at60°-70° C. overnight. The solvent was removed by evaporation at reducedpressure and the residue was taken up in aqueous sodium bicarbonate. Theaqueous solution was washed with ether, and acidified with acqueous HCl.The solid which separated upon acidification was collected byfiltration, dried and recrystallized from methanol to afford 2.5 g (55%)of the desired product as a crystalline solid, mp 224°-226° C. IR and ¹H NMR spectra were in agreement with the assigned structure.

Analysis:

Calculated for C₁₁ H₆ ClF₂ N₅ O₂ S: C, 38.21; H, 1.75; N, 20.26.

Found: C, 38.32; H, 1.44; N, 20.18.

EXAMPLE 64 Preparation of methyl3-methyl-N-(6-methyl-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonyl)-anthranilate

Methyl 3-methylanthranilate (2.1 g, 13 mmol) was dissolved in 4 mlpyridine and 6-methyl-1,2,4-triazolo-[1,5-a]pyrimidine-2-sulfonylchloride was added. After a mild exothermic reaction subsided thereaction mixture was stirred at 50° C. for 24 hours. The pyridine wasremoved by evaporation at reduced pressure and the residue was treatedwith in 10% aqueous sodium bicarbonate. Insoluble material was collectedby filtration, washed with ether and dried to yield 2.9 (63%) of thedesired product as a solid, mp 198.5°-205° C. An analytical sample wasprepared by recrystallization from ethanol to yield a crystalline solid,mp 208.5°-210.5° C. IR and ¹ H NMR spectra were in agreement with theassigned structure.

Analysis: Calculated for C₁₅ H₁₅ N₅ O₄ S: C, 49.85; H, 4.18; N, 19.38.Found: C, 49.96; H, 4.14; N, 19.75.

EXAMPLE 65 Preparation of5-methyl-N-(2,6-difluorophenyl)-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonamide

The starting 2,6-difluoroaniline (18.1 g, 0.140 mol) was dissolved in 45ml of pyridine and 36.1 g (0.155 mol) of5-methyl-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonyl chloride was added.After an exothermic reaction subsided the reaction mixture was stirredat room temperature for 15.5 hours. The pyridine was removed byevaporation at reduced pressure, and the residue was treated with 600 mlof 0.5N NaOH. After stirring to dissolve all soluble material themixture was filtered through celite and the filtrate was acifified with3N HCl. The precipitate which separated upon acidification was collectedby filtration and dried to yield 33.0 g (73%) of the desired product asa pale red solid, mp 245°-247° C. IR and ¹ H NMR spectra were inagreement with the assigned structure.

Analysis: Calculated for C₁₂ H₉ F₂ N₅ O₂ S: C, 44.31; H, 2.79; N, 21.53Found: C, 44.69; H, 2.80; N, 21.85

EXAMPLE 66 Preparation of5,7-dimethyl-N-(2-acetoxymethyl-6-chlorophenyl)-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonamide

A solution of 1.30 gm (6.50 mmol) of 2-amino-3-chlorobenzyl acetate,4.11 gm (52.0 mmol) of pyridine and 5.0 ml of acetonitrile was treatedwith 1.61 gm (6.50 mmol) of5,7-dimethyl-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonyl chloride and theresulting mixture stirred at 25° C. for 120 hours. An additional 0.53 gm(2.2 mmol) of the sulfonyl chloride was added and stirring at 25° C.continued for an additional 24 hours. The mixture was filtered and thefiltrate evaporated to provide a brown oil. The oil was then dissolvedin 40 ml of methylene chloride and stirred with 25 ml of 0.5M NaOH.After 5 minutes, the aqueous phase was separated, washed with ether andacidified with 3N HCl. A light brown solid was collected, washed withwater, dried and recrystallized from acetonitrile to provide 0.35 gm(13%) of the desired product as a solid, mp 214° -217° C., containingapproximately 10% of an impurity. IR and ¹ H NMR spectra were inagreement with the assigned structure.

Analysis: Calculated for C₁₆ H₁₆ ClN₅ O₄ S: C, 46.89; H, 3.94; N, 17.08.Found: C, 46.60; H, 3.80; N, 17.73.

EXAMPLE 67 Preparation of methyl3-amino-2-bromo-4-methyl-N-(5,7-dimethyl-1,2,4-triazolo-[1,5-a]pyrimidine-2-sulfonyl)benzoate

A solution of 1.50 g (6.15 mmol) of methyl2-bromo-3-amino-4-methylbenzoate in 7 ml of pyridine was treated with1.67 g (6.76 mmol) of5,7-dimethyl-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonyl chloride. Afterstirring at 25° C. for 18 hours an additional 0.46 g (1.9 mmol) of thesulfonyl chloride was added and the reaction mixture was heated at52°-55° C. for 3 hours. The solvent was removed by evaporation and theresidue was partitioned between methylene chloride and dilute aqueousHCl. The organic phase was washed with water, dried and evaporated atreduced pressure to yield 1.85 g (66%) of the desired product as ayellow solid upon trituration with ethyl acetate. An analytical samplewas prepared by recrystallization from acetonitrile-DMF to afford acrystalline solid, mp 229°-231° C. IR and ¹ H NMR spectra were inagreement with the assigned structure.

Analysis: Calculated for C₁₆ H₁₆ BrN₅ O₄ S: C, 42.30; H, 3.55; N, 15.41Found: C, 42.29; H, 3.45; N, 15.68

EXAMPLE 68 Preparation of3-amino-2-bromo-4-methyl-N-(5,7-dimethyl-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonyl)benzoicacid

A solution of 2.78 g (6.12 mmol) of methyl3-amino-2-bromo-4-methyl-N-(5,7-dimethyl-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonyl)benzoateand 30 ml of 5% aqueous NaOH in 30 ml of water was stirred at 25° C. for2.5 hours. The reaction mixture was filtered and the filtrate was cooledin ice and acidified to approximately pH 2 with 3N HCl. The solid whichseparated was collected by filtration, washed with water and dried invacuo to yield 2.10 g (78%) of the desired product as a gold solid, mp290° C. (decomposition). IR and ¹ H NMR spectra were in agreement withthe assigned structure.

Analysis: Calculated for C₁₅ H₁₄ BrN₅ O₄ S: C, 40.92; H, 3.21; N, 15.90Found: C, 40.51; H, 3.11; N, 16.01.

EXAMPLE 69 Preparation of5-methylthio-N-(2,6-dichlorophenyl)-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonamide

To 25 ml (13 mmol) of a 0.52M solution of sodium methyl mercaptide inDMSO prepared by bubbling methyl mercaptan into a suspension of sodiumhydride in DMSO, was added 2.6 g (5.9 mmol) of5-(2,2,2-trifluoroethoxy)N-(2,6-dichlorophenyl)-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonamide.The solution was stirred at room temperature for 25 hours, diluted with100 ml of ice water and neutralized with 3N aqueous HCl. The gummy solidwhich separated was collected and taken up in 0.5N aqueous NaOH. Themixture was filtered to remove insoluble material, and the filtrate wasacidified with 6N aqueous HCl. The solid which separated was collectedby filtration and dried to yield 1.5 g (66%) of the desired product as apale yellow solid, mp 239°-243° C. IR and ¹ H NMR spectra were inagreement with the assigned structure.

Analysis: Calculated for C₁₂ H₉ Cl₂ N₅ O₂ S₂ : C, 36.92; H, 2.31; N,17.95. Found: C, 36.51; H, 2.41; N, 17.68.

EXAMPLE 70 Preparation of5-dimethylamino-N-(2,6-dichlorophenyl)-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonamide.

The starting5-(2,2,2-trifluoroethoxy)-N-(2,6-dichlorophenyl)-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonamide(1.5 g, 3.4 mmol) was dissolved in 5 ml (44 mmol) of 50% aqueousdimethylamine. After stirring for 48 hours at room temperature thesolution was diluted with water and acidified with 6N aqueous HCl. Thesolid which separated was collected by filtration and treated with 0.5Naqueous NaOH and filtered to remove insoluble material. The filtrate wasacidified to precipitate a solid. The solid was collected and dried toyield 1.0 g (60%) of the desired product as a solid, mp >310° C. IR and¹ H NMR spectra were in agreement with the assigned structure.

Analysis: Calculated for C₁₃ H₁₂ Cl₂ H₆ O₂ S: C, 40.31; H, 3.10; N,21.71; S, 8.28. Found: C, 40.08; H, 3.05; N, 22.33 S, 7.99.

EXAMPLE 71 Preparation of6-bromo-5-methyl-N-(2,6-dichlorophenyl)-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonamide

A suspension of 4.0 g (11 mmol) of5-methyl-N-(2,6-dichlorophenyl)-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonamidein 50 ml of glacial acetic acid and 10 ml of acetic anhydride wasstirred at 90° C. for 30 minutes. N-Bromosuccinimide (2.4 g, 13 mmol)was added to this hot solution, and the reaction mixture was stirred at90° C. for 60 minutes. The solution was cooled and poured into 200 ml ofice water. A solid which separated was collected and dried. This crudeproduct was purified by dissolving the sample in methylene chloride,filtering the solution through silica gel and triturating the fitratewith pentane. The desired product was obtained as a solid, mp 215°-216°C. IR and ¹ H NMR spectra were in agreement with the assigned structure.

Exact mass calculated for C₁₂ H₈ BrCl₂ N₅ O₂ S: 438.8898 Found: 438.8899

EXAMPLE 72 Preparation of5,7,N-trimethyl-N-(2,6-dichlorophenyl)-1,2,4-triazolo[1,5-a]-pyrimidine-2-sulfonamide

A mixture of 3.00 g (8.06 mmol) of5,7-dimethyl-N-(2,6-dichlorophenyl)-1,2,4-triazolo[1,5-a]-pyrimidine-2-sulfonamideand 0.90 g (8.1 mmol) of potassium t-butoxide in 30 ml of acetonitrilewas heated at reflux for 40 minutes. After cooling to room temperature1.14 g (8.06 mmol) of methyl iodide was added, and the reaction washeated at reflux for 1 hour. After cooling to room temperature, thereaction mixture was diluted with methylene chloride and washed with 1%aqueous NaOH. The organic phase was separated, dried (MgSO₄) andevaporated at reduced pressure. The brown solid residue wasrecrystallized from acetone to give 1.60 g (51%) of the desire productas a tan solid, mp 220°-222° C. IR and ¹ H NMR spectra were in agreementwith the assigned structure.

Analysis:

Calculated for C₁₄ H₁₃ Cl₂ N₅ O₂ S: C, 43.54; H, 3.39; N, 18.13

Found: C, 43.55; H, 3.32; N, 18.03

EXAMPLE 73 Preparation of5-methyl-N-benzoyl-N-(2,6-dichlorophenyl)-1,2,4-triazolo[1,5-a]-pyrimidine-2-sulfonamide

A mixture of 3.00 g (8.37 mmol) of5-methyl-N-(2,6-dichlorophenyl)-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonamideand 1.16 g (8.37 mmol) of anhydrous powdered K₂ CO₃ in 100 ml of acetonewas heated at reflux for 30 minutes. A solution of 1.18 g (8.37 mmol) ofbenzoyl chloride in 10 ml of acetone was added, and the reaction washeated at reflux for 115 min. The reaction was filtered, and thefiltrate was evaporated at reduced pressure. The solid residue wascollected by filtration, washed thoroughly with aqueous NaHCO₃ and H₂ Oand dried to yield 2.75 g (72%) of the desired product as a solid, mp187°-189° C. IR and ¹ H NMR spectra were in agreement with the assignedstructure.

Analysis:

Calculated for C₁₉ H₁₃ Cl₂ N₅ O₃ S: C, 49.36; H, 2.83; N, 15.15.

Found: C, 48.97; H, 2.84; N, 15.16

EXAMPLE 74 Preparation of5-methyl-N-(2,6-dichlorophenyl)-4,5,6,7-tetrahydro-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonamide

Sodium borohydride (0.6 g, 16 mmol) was added to a solution of 3.0 g(8.3 mmol) of5-methyl-N-(2,6-dichlorophenyl)-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonamidein 25 ml of dry DMSO. An exothermic reaction occurred and 2.0 ml (31mmol) of methanesulfonic acid in 5 ml of DMSO was added at a rate tomaintain the temperature of the reaction mixture at 60° C. After theaddition was complete the reaction mixture was stirred for 10 minutesand carefully quenched with 0.5N aqueous NaOH. The clear yellow solutionwas filtered, and the filtrate was acidified with 3N aqueous HCl. Theresutling precipitate was treated with dilute aqueous NaOH and filteredto remove insoluble material. The filtrate was acidified with aqueousHCl to precipitate a solid. The solid was collected by filtration anddried to yield 1.11 g (37%) of the desired product as a solid, mp230°-235° C. IR and ¹ H NMR spectra were in agreement with the assignedstructure.

Analysis:

Calculated for C₁₂ H₁₂ Cl₂ N₅ O₂ S: C, 39.89; H, 3.32; N, 19.39.

Found: C, 39.72; H, 3.42; N, 19.19.

EXAMPLE 75 Preparation ofN-(2,6-dichloro-3-methylphenyl)-5-amino-1,2,4-triazole-3-sulfonamide

Potassium hydroxide (72.9 g of 85 percent pellets, 1.20 mol) wasdissolved in one liter of water in a 2 liter round bottom flask and113.3 g (0.30 mol) of wetN-(2,6-dichloro-3-methylphenyl)-5,7-dimethyl-1,2,4,-triazolo[1,5-a]pyrimidine-2-sulfonamidewas added with stirring. The mixture obtained was cooled to 17° C. and100 ml of 30 percent hydrogen peroxide solution (about 1 mole) was addedwith stirring over a 0.5 hour period so that the temperature did notexceed 40° C. The reaction was found to be complete after three hours byhigh pressure liquid chromatography. An aqueous solution of sodiumbisulfite was added to quench the excess hydrogen peroxide and thesolution obtained was filtered through celite and then acidified withconcentrated hydrochloric acid. The precipitate that formed wascollected by filtration, washed with water, and partially dried. Thismaterial, which is the N¹ -acetyl derivative of the desired product, wasdissolved in 800 ml of tetrahydrofuran and the resulting solution wascombined with 100 ml of water and 100 ml of concentrated hydrochloricacid. This mixture was heated at reflux with stirring in a two literround bottom flask overnight. The solvent was removed by evaporationunder reduced pressure and the resulting aqueous suspension was filteredto collect the solid product. This was washed with water and dried toobtain 59.3 g (61 percent of theory) of the title compound as a whitesolid. This compound has an m.p. of 206°-8° C.

Analysis:

Calculated for C₉ H₉ Cl₃ N₅ O₂ S: C, 30.1; H, 2.81; N, 19.3.

Found: C, 29.9; H, 3.33; N, 19.0.

EXAMPLE 76 Preparation ofN-(2-trifluoromethylphenyl)-5-amino-1,2,4-triazole-3-sulfonamide

A 110.6 g (0.30 mol) portion ofN-(2-trifluoromethylphenyl)-5,7-dimethyl-1,2,4,-triazolo[1,5-a]pyrimidine-2-sulfonamidewas added to a solution of 79 g of 85 percent potassium hydroxide (1.2mol) in two liters of water. Another liter of water was added and then400 ml of 30 percent hydrogen peroxide (3.9 moles) was added to themixture with stirring and cooling with an ice bath at a rate so that thetemperature did not exceed 40° C. After about 3.5 hours, the reactionwas found to be complete by thin layer chromatography. About 100 ml of12N hydrochloric acid was added dropwise to precipitate the product andthen a little solid sodium bisulfite was added to destroy the excesshydrogen peroxide. The precipitate was collected by filtration washedwith water and dried to obtain 94 g of the N¹ -acetyl derivative of thedesired product. This was dissolved in 750 ml of tetrahydrofuran and 375ml of concentrated hydrochloric acid and 360 ml of water were added. Themixture was heated to reflux with stirring for about four hours. Thesolvent was then removed by evaporation under reduced pressure. Ethanolwas added and the solution obtained was treated with charcoal. Ethanolwas evaporated to precipitate the title compound which was collected byfiltration and dried to obtain a total of 51.6 g (56.4 percent oftheory) of white solid, the first 47.6 g of which melted at 227°-9° C.

Analysis:

Calculated for C₉ H₈ N₅ F₃ SO₂ : C, 35.18; H, 2.62; N, 22.80; S, 10.43.

Found: C, 34.79; H, 2.65; N, 22.53; S, 10.20.

EXAMPLE 77 Preparation ofN-(2,6-dichloro-3-methylphenyl)-7-hydroxy-5-methyl-1,2,4-triazolo[1,5-a]-pyrimidine-2-sulfonamide

A solution of 32.2 g (0.10 mol) ofN-(2,6-dichloro-3-methylphenyl)-5-amino-1,2,4-triazole-3-sulfonamide and14 ml (0.11 mol) of ethyl acetoacetate in 500 ml of methanol containing1 ml of 12N hydrochloric acid was heated to reflux with stirring forabout 18 hours. The solid present was collected by filtration and thefiltrate was heated to reflux for another day. The mixture obtained wascooled in an ice bath and the solid present was collected by filtration.The filtrate was concentrated to about 200 ml by evaporation of methanoland heated to reflux overnight. The mixture obtained was filtered tocollect the solid present. The filtrate was concentrated to about 150ml, treated with about 2 ml of ethyl acetoacetate, and heated at refluxfor about 3 days. The solids present were collected by filtration anddried to obtain 6.4 g, 10.0 g, 8.2 g and 11.1 g crops of the titlecompound for a total of 35.7 g (92 percent of theory). The firstobtained crop melted at 346°-7° C. with decomposition.

Analysis:

Calculated for C₁₃ H₁₁ Cl₂ N₅ O₃ S: C, 40.2; H, 2.86; N, 18.04

Found: C, 39.6; H, 2.96; N, 17.96

EXAMPLE 78 Preparation ofN-(2-trifluoromethylphenyl)-7-hydroxy-5-methyl-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonamide

A solution of 1 ml of 12N hydrochloric acid in 250 ml of methanol wasadded to a mixture of 20.0 g (65.1 mmol) ofN-(2-trifluoromethylphenyl)-5-amino-1,2,4-triazole-3-sulfonamide and 9.2ml (72.2 mmol) of ethyl acetoacetate and the mixture heated to refluxwith stirring. After about 5 days, most but not all of the startingmaterial was found to have reacted by thin layer chromatography. Thesolution was chilled and the precipitate that formed was collected byfiltration, washed with cold methanol and dried to obtain 16.5 g (67.9percent of theory) of the title compound as a white solid hemihydratemelting at 245°-7° C.

Analysis:

Calculated for C₁₃ H₁₀ F₃ N₅ O₃.1/2H₂ O: C, 40.8; H, 2.88; N, 18.31; S,8.37.

Found: C, 40.4; H, 2.76; N, 18.29; S, 7.93

EXAMPLE 79 Preparation ofN-(2,6-dichloro-3-methylphenyl)-7-chloro-5-methyl-1,2,4-triazolo-[1,5-a]pyrimidine-2-sulfonamide

A solution of 100 ml of phosphoryl chloride in 400 ml of dryacetonitrile was added to 12.0 g (30.9 mmol) ofN-(2,6-dichloro-3-methylphenyl)-7-hydroxy-5-methyl-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonamideand heated to reflux with stirring. After about 24 hours, the mixturebecame a solution which appeared to contain little or no startingmaterial by thin layer chromatography. The volatiles were largelyremoved by evaporation under reduced pressure and the residue pouredonto about one liter of ice and water with stirring using freshacetonitrile as a transfer solvent. The solid in the resulting mixturewas collected by filtration, washed with water, and dried under reducedpressure at 70° C. overnight. The resulting solid, which was found to bethe title compound by NMR analysis, amounted to 8.4 g (67 percent oftheory).

EXAMPLE 80 Preparation ofN-(2-trifluoromethylphenyl)-7-chloro-5-methyl-1,2,4-triazolo[1,5-a]pyridmidine-2-sulfonamide

Phosphorus oxychloride (135 ml, 1.47 mol) was diluted with 335 ml of dryacetonitrile and added to 15 g (40 mmol) ofN-(2-trifluoromethylphenyl)-7-hydroxy-5-methyl-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonamidein a one liter flask and heated to reflux with stirring.

After about 3 days, the reaction was found to be complete by thin layerchromatography. Volatiles were removed by evaporation under reducedpressure until the mixture became very viscous and the residue waspoured onto about one liter of ice and water with stirring. After about30 minutes, the solid that formed was collected by filtration, washedwith ice water, and dried under reduced pressure at room temperature. Itwas then dissolved in methylene chloride and the resulting solutiondried over magnesium sulfate for about five minutes and filtered. Thevolatiles were removed from the filtrate by evaporation under reducedpressure to obtain the title compound as a white solid residue. Theproduct, the structure of which was confirmed by NMR analysis, amountedto 13.4 g (85.4 percent of theory).

EXAMPLE 81 Preparation ofN-(2,6-dichloro-3-methylphenyl)-7-methoxy-5-methyl-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonamide

Sodium (0.6 g, 26 mmol) was added to about 40 ml of methanol and allowedto react.N-(2,6-dichloro-3-methylphenyl)-7-chloro-5-methyl-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonamide(2.5 g, 6.9 mmol) was added with stirring. After about 90 minutes, thinlayer chromatography indicated the starting material had reacted. Thesolution was then acidified by adding 6N hydrochloric acid dropwise andthen concentrated by evaporation under reduced pressure. The residue wastriturated with water and the solid that formed was washed with waterand dried to obtain 1.35 g of the title compound as a white solid, m.p.239°-42° C.

Analysis: Calculated for C₁₄ H₁₃ Cl₂ N₅ O₃ : C, 41.8; H, 3.26; N, 17.41;S, 7.97. Found: C, 41.4; H, 3.19; N, 17.42; S, 8.15.

EXAMPLE 82 Preparation ofN-(2,6-dichloro-3-methylphenyl)-7-ethoxy-5-methyl-1,2,4-triazolo[1,5-a]pyridimidine-2-sulfonamide

Sodium (0.69 g, 30 mmol) was added to about 5 ml of ethanol and allowedto react. The mixture was allowed to cool and then 4.0 g (9.8 mmol) ofN-(2,6-dichloro-3-methylphenyl)-7-chloro-5-methyl-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonamidewas added with stirring. After 15 minutes no starting material remainedby thin layer chromatographic analysis although complete solution wasnever attained. The mixture was acidified with 6N hydrochloric acid andconcentrated under reduced pressure. The residue was triturated withwater and the solid removed by filtration and washed with water. It wasthen dissolved in aqueous sodium hydroxide using a minimum amount of thebase and the aqueous solution was twice extracted with ether andacidified with 6N hydrochloric acid. The solid that formed was collectedby filtration, washed with water, and dried. This was extracted withabout 500 ml of boiling chloroform. The chloroform solution wasconcentrated to about 150 ml and allowed to cool to form a precipitatewhich was collected by filtration and dried to obtain 1.7 g (42 percentof theory) of the title compound as a white solid, m.p. 228°-9° C.

Analysis: Calculated for C₁₅ H₁₅ Cl₂ N₅ O₃ S: C, 43.3; H, 3.63; N,16.83; S, 7.70. Found: C, 42.9; H, 3.66; N, 16.92; S, 7.66.

EXAMPLE 83 Preparation ofN-(2,6-dichlorophenyl)-7-methylthio-5-methyl-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonamide

An oil dispersion of sodium hydride (1.15 g, 24 mmol) was washed threetimes with hexane by slurrying and decanting and was then suspended in30 ml of dry dimethyl sulfoxide. An excess of methanethiol (greater than1.3 ml) was added dropwise with stirring. A solution ofN-(2,6-dichlorophenyl)-7-chloro-5-methyl-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonamide(3.14 g, 8.0 mmol) was added to this dropwise with stirring. Thirtyminutes after the addition was complete, about 200 ml of water wereadded and the solution was acidified with 6N hydrochloric acid. Nitrogenwas blown through the system to remove any unreacted methanethiol(trapped in sodium hypochlorite solution) and the solid present wascollected by filtration, washed with water, and dried to obtain 2.7 g(84 percent by theory) of the title compound contaminated with some5-hydroxy analog. A 1 g portion of this was dissolved in aqueous sodiumhydroxide (minimum amount of base) and the resulting solution wastreated with charcoal, filtered, and then acidified with 6N hydrochloricacid. The resulting precipitate was collected by filtration, washed withwater, and dried to obtain 0.9 g of the title compound melting at289°-91° C.

Analysis: Calculated for C₁₃ H₁₁ Cl₂ N₅ O₂ S₂ C, 38.6; H, 2.74; N,17.32. Found: C, 38.4; H, 2.65; N, 17.20.

EXAMPLE 84 Preparation ofN-(2-trifluorophenyl)-7-methylthio-5-methyl-1,2,4-triazolo[1,5-a]-pyrimidine-2-sulfonamide

Sodium hydride (1.2 g, 25 mmol) was washed three times with hexane andsuspended in 50 ml of dry dimethyl sulfoxide. An excess of methanethiol(greater than 1.4 ml) was added dropwise until a clear solution formed.The solution was allowed to cool and then 2.5 g (6.4 mmol) ofN-(2-trifluorophenyl)-7-chloro-5-methyl-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonamidewas added. After a short time, the starting material was found to beconsumed using thin layer chromatography and the solution was dilutedwith water and acidified with hydrochloric acid. Nitrogen was blownthrough the solution to remove any unreacted methanethiol. The solids inthe resulting mixture were collected by filtration, washed with water,dissolved in dilute aqueous sodium hydroxide, and reprecipitated with 6Nhydrochloric acid. The solid was collected by filtration, washed withwater, and dried to obtain 1.4 g (54 percent of theory) of the titlecompound contaminated with some hydroxy analog and melting at 184°-9° C.A portion of this was extracted with boiling chloroform and thechloroform solution was concentrated by evaporation and then dilutedwith carbon tetrachloride and cooled to precipitate the title compound.This melted at 193°-200° C. after collection and drying.

Analysis: Calculated for C₁₄ H₁₂ F₃ N₅ O₂ S₂ : C, 41.7; H, 3.00; N,17.36; S, 15.90. Found: C, 41.4; H, 2.95; N, 17.21 S, 15.65.

EXAMPLE 85 Preparation ofN-(2,6-dichloro-3-methylphenyl)-5,7-dihydroxy-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonamide

Sodium (3.11 g, 135 mmol) was added to 250 ml of absolute ethanol in a500 ml round bottom flask and allowed to react under nitrogen.N-(2,6-dichloro-3-methylphenyl)-5-amino-1,2,4-triazole-3-sulfonamide(14.5 g, 45 mmol) and then dimethyl malonate (11.9 g, 90 mmol) wereadded and the mixture heated at reflux with stirring for about threedays. The mixture was then cooled with an ice bath and filtered tocollect the solids. These were washed with hexane and dissolved in about75 ml of cold water and the resulting solution was acidified to about pH2 with conc. hydrochloric acid. The precipitate that formed wascollected by filtration and dried to obtain 13.55 g (77.1 percent oftheory) of the title compound as a white powder, which decomposes above200° C. This was shown to be the title compound by NMR.

EXAMPLE 86 Preparation ofN-(2-methoxy-6-trifluoromethylphenyl)-5,7-dihydroxy-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonamide

Sodium (5.90 g, 257 mmol) was added to 250 ml of absolute ethanol undernitrogen and allowed to react. A 28.67 g, 85.0 mmol sample ofN-(2-methoxy-6-trifluoromethylphenyl)-5-amino-1,2,4-triazole-3-sulfonamideand 24.46 g (170 mmol) of dimethyl malonate were added and the mixtureheated at reflux with stirring for two days. It was then cooled with anice bath and the solids present were collected by filtration and washedwith hexane. They were then dissolved in about 150 ml of ice water andacidified with conc. hydrochloric acid to obtain 11.95 g, the titlecompound, which was collected by filtration and dried. The ethanolicsolution was concentrated by evaporation and dried by adding toluene andremoving volatiles by evaporation under reduced pressure three times.The residue was taken up in ethanol and treated as before with sodiumand 16.85 g of dimethyl malonate to obtain another 10.26 g of the titlecompound. A total of 22.21 g (64.5 percent of theory) of the titlecompound, which melts at 237°-243° C. with decomposition, was obtained.

EXAMPLE 87 Preparation ofN-(2,6-dichloro-3-methylphenyl)-5,7-dichloro-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonamide

29.27 g (75 mmol) sample ofN-(2,6-dichloro-3-methylpheny)-5,7-dihydroxy-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonamidewas added to 250 ml of phosphorus oxychloride and 5.0 g of phosphoruspentachloride and the mixture was heated to reflux with stirring. After2.5 hours the mixture was allowed to cool and, after standing overnight,it was further cooled in an ice bath. The solids present were removed byfiltration, washed with cold toluene, triturated with cold water, anddried to obtain 11.76 g (37 percent of theory) of the title compound;m.p. 269°-271° C. Additional material was recovered from the phosphorusoxychloride by the addition of water.

Analysis: Calculated for C₁₂ H₇ Cl₄ NO₂ S: C, 33.8; H, 1.65; N, 16.40.Found: C, 33.9; H, 1.70; N, 16.56.

EXAMPLE 88 Preparation ofN-(2-methoxy-6-trifluoromethylphenyl)-5,7-dichloro-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonamide

A 2.03 g (5.0 mmol) sample ofN-(2-methoxy-6-trifluoromethylphenyl)-5,7-dihydroxy-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonamidewas combined with 15 ml of phosphorus oxychloride and the mixture heatedto reflux with stirring for eight hours. The mixture was allowed to cooland the solids present were collected by filtration and washed with coldtoluene. They were then washed with water and dried to obtain 0.55 g(24.9 percent of theory) of the title compound. This material washomogeneous by chromatography and its NMR spectrum was compatible withthe assigned structure. Additional product was obtained by quenching thephosphorus oxychloride solution with ice water.

EXAMPLE 89 Preparation ofN-(2,6-dichloro-3-methylphenyl)-5,7-dimethoxy-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonamide

Sodium (469 mg, 20.4 mmol) was added to 25 ml of methanol under nitrogenand allowed to react. The resulting solution was allowed to cool andthen 2.14 g (5.0 mmol) ofN-(2,6-dichloro-3-methylphenyl)-5,7-dichloro-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonamide were added with stirring. After about onehour, 1 ml of acetic acid was added and the mixture was poured intoabout 150 ml of ice water. The solid present was collected by filtrationand dried to obtain 1.76 g (84.2 percent of theory) of the titlecompound as a white powder, m.p. 218°-221° C.

Analysis: Calculated for C₁₄ H₁₃ Cl₂ N₅ O₄ S: C, 40.2; H, 3.13; N,16.74. Found: C, 39.9; H, 3.15; N, 16.76.

EXAMPLE 90 Preparation ofN-(2,6-dichlorophenyl)-5,7-dimethoxy-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonamide

Sodium (683 mg, 29.7 mmol) was added to 30 ml of methanol under nitrogenand allowed to react. The resulting solution was cooled and 4.06 g (9.83mmol) ofN-(2,6-dichlorophenyl)-5,7-dichloro-1,2,4-triazolo[1,5-a]-pyrimidine-2-sulfonamidewere added with stirring. After one hour, 2 ml of acetic acid was addedand the mixture was poured into about 150 ml of ice water. The solidspresent were collected by filtration and dried to obtain 3.21 g (88percent of theory) of the title compound, which is a white powder thatmelts at 232°-4° C.

EXAMPLE 91 Preparation of methyl 3-amino-2,4-dichlorobenzoate

This material was prepared by chlorination of methyl3-amino-4-chlorobenzoate with N-chlorosuccinimide. The product wasisolated as a solid, m.p. 50°-52° C. The product was characterized by IRand ¹ H NMR spectroscopy and combustion analysis.

EXAMPLE 92 Preparation of methyl 3-amino-2-bromo-4-methylbenzoate

A mixture of 16.5 g (100 mmol) of methyl 3-amino-4-methylbenzoate and300 ml of CCl₄ was treated with 18.6 g (105 mmol) of N-bromosuccinimideand stirred at ambient temperature for four hours. The reaction mixturewas filtered, and the filtrate was evaporated at reduced pressure toafford an amber oil. To remove material resulting from bromination atthe 6-position, the crude product was taken up in 100 ml of hexane and60 ml of ether and treated with 3.96 g (50.0 mmol) of pyridine and 3.06g (30.0 mmol) of acetic anhydride. After stirring for three hours at 25°C., the precipitate was removed by filtration. The filtrate wasevaporated at reduced pressure to yield an amber oil. The crude productwas purified by HPLC to afford 14.5 g (59%) of the desired product as anamber oil. IR and ¹ H NMR spectra were in agreement with the assignedstructure.

Analysis: Calculated for C₉ H₁₀ BrNO₂ : C, 44.29; H, 4.13; N, 5.74Found: C, 44.14; H, 3.96; N, 5.72

EXAMPLE 93 Preparation of methyl 3-methyl-4-chloroanthranilate

This material was prepared by esterification of the correspondinganthranilic acid with HCl in methanol. The product was isolated as asolid, mp 72°-74° C.

EXAMPLE 94 Preparation of 2,6-dichloro-3-trifluoromethylaniline

This material was prepared by chlorination of2-chloro-5-trifluoromethylaniline with N-chlorosuccinimide followed bychromatographic purification. The product was isolated as a yellow oilwhich was characterized by IR and ¹ H NMR spectroscopy and combustionanalysis.

EXAMPLE 95 Preparation of 4-bromo-2,3-dichloro-6-methylaniline

This material was prepared from 4-bromo-5-chloro-2-methylaniline bychlorination with N-chlorosuccinimide. The product was isolated as asolid, m.p. 66°-68° C. The product was characterized by IR and ¹ H NMRspectroscopy and combustion analysis.

EXAMPLE 96 Preparation of 2,3-dichloro-6-methylaniline

A slurry of 6.50 g (25.5 mmol) of 2,3-dichloro-4-bromo-6-methylanilineand 8.37 g (102 mmol) of sodium acetate in 120 ml of acetic acid-ethanol(1:1, v/v) was treated with 0.65 g of 5% palladium on carbon. Themixture was hydrogenated in a Parr hydrogenation apparatus at an initialpressure of 50 psi for 10 minutes. The reaction mixture was filtered,and the filtrate was concentrated by evaporation at reduced pressure.The residue was partitioned between ether and water, and the organiclayer was washed with 5% aqueous sodium hydroxide, dried and evaporatedat reduced pressure. The residue was purified by Kugelrohr distillationto afford 4.00 g (89% of the desired product as a colorless oil, b.p.60°-70° C. (0.15 mm). IR and ¹ H NMR spectra were in agreement with theassigned structure.

Analysis: Calculated for C₇ H₇ Cl₂ N: C, 47.76; H, 4.01; N, 7.95. Found:C, 48.11; H, 4.04; N, 8.19.

EXAMPLE 97 Preparation of 2-amino-3-chlorobenzyl alcohol

A solution of 28.9 g (155 mmol) of methyl 3-chloroanthranilate in 100 mlof ether was added dropwise to a stirred suspenson of 7.67 g (202 mmol)of lithium aluminum hydride in 400 ml of ether. After stirring for fivehours at room temperature, the grey mixture was treated sequentiallywith 7.7 ml of water, 7.7 ml of 15% sodium hydroxide and 23 ml of water.The reaction mixture was filtered, and the filtrate was evaporated atreduced pressure. The oily residue was dissolved in ether, andprecipitation of the product was induced by addition of hexane. Theproduct was collected by filtration to yield a tan solid in 67% yield,mp. 56°-68° C. IR and ¹ H NMR spectra were in agreement with theassigned structure.

Analysis:

Calculated for C₇ H₈ ClNO: C, 53.35; H, 5.12; N, 8.88.

Found: C, 53.16; H, 4.84; N, 9.28.

EXAMPLE 98 Preparation of 2-chloro-6-methoxymethylaniline

A solution of 4.00 g (25.4 mmol) of 2-amino-3-chlorobenzyl alcohol in 30ml of dry THF was cooled to -78° C., treated with 16.7 ml (26.7 mmol) of1.60M n-butyllithium in hexane, warmed to 0°-5° C., treated with 3.61 g(25.4 mmol) of methyl iodide and heated at reflux for 5.5 hours. Thesolvent was removed by evaporation at reduced pressure. The residue waspartitioned between 175 ml of ether and water, and the organic phase wasseparated and dried (MgSO₄). The solvent was removed by evaporation atreduced pressure, and the residue was purified by HPLC eluting withEtOAc (5:95, v/v) to afford 1.1 g of the desired product as a pale brownoil. IR and ¹ H NMR spectra were in agreement with the assignedstructure.

Analysis:

Calculated for C₈ H₁₀ ClNO: C, 56.00; H, 5.87; N, 8.16.

Found: C, 56,25; H, 5.98; N, 8.28.

EXAMPLE 99 Preparation of 2-acetoxymethyl-6-chloroaniline

This material was prepared from 2-amino-3-chlorobenzyl alcohol andacetyl chloride by the general procedure outlined in Example 98. Theproduct was isolated as an amber oil and was characterized by IR and 'HNMR spectroscopy and combustion analysis.

EXAMPLE 100 Preparation of 2-benzyloxymethyl-6-chloroaniline

This material was prepared from 2-amino-3-chlorobenzyl alcohol andbenzyl bromide by the general procedure outlined in Example 98. Theproduct was purified by Kugelrohr distillation to yield an oil, b.p.118°-125° C. (0.1 mm). The product was characterized by IR and ¹ H NMRspectroscopy.

EXAMPLE 101 Preparation of N-n-butoxycarbonyl-2-fluoroaniline

A solution of 2-fluoroaniline (30.0 g, 0.27 mol) and di-t-butylcarbonate (66.5 g, 0.30 mol) in 100 ml of THF was heated at reflux for 4hours. The solvent was removed by evaporation at reduced pressure, andthe residue was partitioned between 1M aqueous citric acid and ethylacetate. The organic phase was washed with saturated aqueous NaCl. Thesolvent was removed to afford the desired product, which was usedwithout further purification. IR and ¹ H NMR spectra were in agreementwith the assigned structure.

Analysis:

Calculated for C₁₁ H₁₄ FNO₂ : C, 62.55; H, 6.68; N, 6.63.

Found: C, 62.45; H, 6.39; N, 6.21.

EXAMPLE 102 Preparation of 2-fluoro-6-methylaniline

A solution of 8.15 g (38.5 mmol) of N-t-butoxycarbonyl-2-fluoroanilinein 30 ml of dry THF was cooled to -70° C., and 46.3 ml (93 mmol) of 2.0Mt-butyllithium in pentane was added dropwise at a rate sufficient tomaintain the temperature below -65° C. When the addition was completethe reaction mixture was stirred at -70° C. for 15 minutes, warmed to-20° C. and stirred for 2.5 hours. A solution of 6.8 g (30 mmol) ofmethyl iodide in THF was added and the reaction was allowed to warm toroom temperature. The reaction mixture was partitioned between ether andwater, and the organic layer was washed with saturated aqueous NaCl anddried (MgSO₄). Evaporation at reduced pressure gave a yellow solid whichwas added to 25 ml of 3N HCl and heated at reflux for 3 hours. Aftercooling to room temperature the pH of the solution was adjusted to pH 7,and the solution was extracted twice with methylene chloride. Thecombined organic phases were washed with water and dried (MgSO₄).Evaporation at reduced pressure gave a yellow oil which was Kugelrohrdistilled to yield 3.8 g (80%) of the desired product as a liquid, b.p.91°-93° C. (0.1 mm). IR and ¹ H NMR spectra were in agreement with theassigned structure.

Analysis:

Calculated for C₇ H₈ FN: C, 67.20; H, 6.45; N, 11.20.

Found: C, 67.61; H, 6.09; N, 11.53.

EXAMPLE 103 Preparation of 2-fluoro-6-methylthioaniline

This material was prepared for N-t-butoxycarbonyl-2-fluoroaniline anddimethyl disulfide following the general procedure outlined in Example102. IR and ¹ H NMR spectra of the product were consistent with theassigned structure.

EXAMPLE 104 Preparation of2-(2-chloro-4-trifluoromethylphenoxy)nitrobenzene

A mixture of 29.4 g (0.200 mol) of 2-fluoronitrobenzene, 41.0 g (0.200mol) of 2-chloro-4-trifluoromethylphenol and 30.0 g (0.220 mol) of K₂CO₃ in 150 ml of DMSO was heated at 100° C. for six hours. The reactionmixture was poured over ice and extracted with ether. The organic phasewas washed with water and saturated aqueous NaCl and dried (MgSO₄). Thesolvent was removed by evaporation at reduced pressure to yield 56.1 g(88%) of the desired product as a yellow oil. IR and ¹ H NMR spectrawere in agreement with the assigned structure.

Analysis:

Calculated for C₁₃ H₇ ClF₃ NO₃ : C, 49.15; H, 2.22; N, 4.41.

Found: C, 49.47; H, 2.07; N, 4.13.

EXAMPLE 105 Preparation of 2-(2-chloro-4-trifluoromethylphenoxy)aniline

Raney Nickel (4.0 g) was washed with water and added to 250 ml ofethanol. To this mixture under a nitrogen blanket was added 56 g (0.18mol) of 2-(2-chloro-4-trifluoromethyl)phenoxynitrobenzene. This mixturewas hydrogenated in a Parr hydrogenation apparatus at an initialpressure of 50 psi. The catalyst was removed by filtration throughcelite and the filtrate was evaporated at reduced pressure to yield 49.9g (100%) of the desired product as an amber oil. IR and ¹ H NMR spectrawere in agreement with the assigned structure.

Analysis:

Calculated for C₁₃ H₉ ClF₃ NO: C, 54.27; H, 3.15; N, 4.87.

Found: C, 54.72; H, 3.01; N, 4.61.

EXAMPLE 106 Preparation of2-(3-chloro-5-trifluoromethyl-2-pyridyloxy)nitrobenzene

This material was prepared in 63% yield from3-chloro-2-fluoro-5-trifluoromethylpyridine and 2-nitrophenol followingthe general procedure outlined in Example 104. The product was isolatedas an amber oil which was characterized by IR and ¹ H NMR spectroscopy.

EXAMPLE 107 Preparation of2-(3-chloro-5-trifluoromethyl-2-pyridyloxy)aniline

This material was prepared in 61% yield by hydrogenation of2-(3-chloro-5-trifluoromethyl-2-pyridyloxy)nitrobenzene following thegeneral procedure outlined in Example 105. The crude product wasrecrystallized from hexane to yield the desired product as whiteneedles, mp 133°-135° C. IR and ¹ H NMR spectra were in agreement withthe assigned structure.

Analysis:

Calculated for C₁₂ H₈ ClF₃ N₂ O: C, 49.94; H, 2.79; N, 30.50.

Found: C, 49.93; H, 2.91; N, 30.27.

EXAMPLE 108 Preparation of2-(2-chloro-4-trifluoromethylphenoxy)-6-fluoronitrobenzene

This material was prepared in 47% yeild from 2,6-difluoronitrobenzeneand 2-chloro-4-trifluoromethylphenol following the general procedureoutlined in Example 104. The product was isolated as an oil which wascharacterized by IR and ¹ H NMR spectroscopy.

EXAMPLE 109 Preparation of2-(2-chloro-4-trifluoromethylphenoxy)-6-fluoroaniline

This material was prepared in 72% yield by hydrogenation of2-(2-chloro-4-trifluoromethylphenoxy)-6-fluoronitrobenzene following thegeneral procedure outlined in Example 105. The crude product wasKugelrohr distilled to yield the desired product as a liquid, bp102°-103° C. (10 mm). IR and 'H NMR spectra were in agreement with theassigned structure.

Analysis:

Calculated for C₁₃ H₈ ClF₄ NO: C, 51.09; H, 2.64; H, 9.17.

Found: C, 51.34; H, 2.41; H, 9.16.

EXAMPLE 110 Preparation of 6-methoxy-2-trifluoromethylbenzoic acid

A solution of 3-trifluoromethylanisol (50.0 g, 0.28 mole) intetrahydrofuran was cooled to -78° C. under nitrogen atmosphere withstirring. To this solution was added n-butyl lithium (114 ml of 2.5M,0.28 mole), dropwise at such a rate that the temperature did not exceed-65° C. When the addition was complete, the mixture was stirred at -78°l C. for three hours. The mixture was then poured over a slurry of dryice/ether and allowed to come to room temperature. The solvent wasremoved under reduced pressure to give a white solid. This solid wasdissolved in a minimum amount of water, extracted with diethyl ether(2×100 ml) and the aqueous phase was acidified to pH 2 with dilutehydrochloric acid. An oil formed and was extracted with diethyl ether,washed several times with water and dried over magnesium sulfate. Thesolvent was removed to give 45.6 g (74 percent of theory) of the titlecompound as a white solid of m.p. 129°- 130° C.

Analysis:

Calculated for C₉ H₇ F₃ O₃ : C, 49.11; H, 3.21.

Found: C, 49.08; H, 3.21.

EXAMPLE 111 Preparation of 6-methoxy-2-trifluoromethylbenzamide

A mixture of 6-methoxy-2-trifluoromethylbenzamide (40.0 g, 0.18 mol) inthionyl chloride (50 ml, 0.48 mol) was heated under reflux for threehours. The formed hydrogen chloride was neutralized in an aqueous sodiumhydroxide trap. When the evolution of hydrogen chloride stopped, themixture was cooled to room temperature and the excess thionyl chloridewas removed by evaporation under reduced pressure. The resulting acidchloride was added dropwise with vigorous stirring to 250 ml of 12Nammonium hydroxide while cooling to 0° C. in a salt/ice bath. When theaddition was complete, the mixture was allowed to warm to ambienttemperature and stir for an additional two hours. The solid that formedwas collected by filtration, dried under vacuum and recrystallized frommethylcyclohexane to give 32.4 g (82 percent of theory) of the titlecompound as a white solid of m.p. 178°-181° C.

Analysis:

Calculated for C₉ H₈ F₃ NO₂ : C, 49.31; H, 3.68; N, 6.39.

Found: C, 49.05; H, 3.79; N, 6.34.

EXAMPLE 112 Preparation of 6-methoxy-2-trifluoromethylaniline

Sodium hydroxide (4.6 g, 0.11 mol) was dissolved in 50 ml of water andthe solution was cooled to 0° C. in a salt/ice bath. Bromine (5.87 g, 37mmol) was slowly added to this solution and allowed to stir at 0° C. for15 minutes. To this rapidly stirred solution was added in portions6-methoxy-2-trifluoromethylbenzamide (6.4 g, 30.0 mmol) keeping thetemperature below 5° C. The mixture was stirred at 0° C. for three hoursand then heated to reflux for two hours. It was then allowed to cool toambient temperature and was extracted with methylene chloride (2×100ml). The organic phase was combined and dried over magnesium sulfate.The solvent was removed under reduced pressure and the resulting amberliquid distilled to give 4.1 g (71 percent of theory) of the titlecompound as a clear, colorless oil, b.p. 56° C. at 0.7 mm Hg.

Analysis:

Calculated for C₈ H₈ F₃ NO: C, 50,28; H, 4.22; N, 7.33.

Found: C, 50.24; H, 4.12; N, 7.03.

EXAMPLE 113 Preparation of 6-fluoro-2-trifluoromethylbenzoic acid

A mixture of 3-fluorobenzotrifluoride (25.0 g, 0.15 mol) intetrahydrofuran (200 ml) was cooled to -78° C. in a dry ice/acetone bathunder nitrogen atmosphere. To this solution was added dropwise withrapid stirring N-butyl lithium (1.6M, 95.2 ml) at such rate that thetemperature did not exceed -60° C. When the addition was complete, themixture was allowed to stir at -78° C. for an additional five hours. Themixture was then poured over a slurry of dry ice/ether and allowed tocome to room temperature. The solvent was removed by evaporation underreduced pressure to obtain a white solid residue. This solid wasdissolved in a minimum amount of water, the solution was extracted withdiethyl ether (2×100 ml) and the aqueous phase was acidified to pH 2with dilute hydrochloric acid. An oil formed and this was dissolved indiethyl ether; the solution was washed several times with water anddried over magnesium sulfate. The solvent was removed by evaporationunder reduced pressure to give a white solid. NMR analysis indicatedthis product was a mixture of the title compound and an isomer. A yieldof 15.6 g (50 percent of theory) was obtained.

Analysis:

Calculated for C₈ H₄ F₄ O₂ : C, 46.17; H, 1.94.

Found: C, 46.29; H, 1.73.

EXAMPLE 114 Preparation of 6-fluoro-2-trifluoromethylbenzamide

A mixture of 6-fluoro-2-trifluoromethylbenzoic acid and its isomer (19.6g, 0.10 mol) and thionyl chloride (35 ml) was heated under reflux fortwo hours. The hydrogen chloride formed was neutralized in an aqueoussodium hydroxide trap. When the evolution of hydrogen chloride stopped,the mixture was cooled to room temperature and the excess thionylchloride was removed by evaporation under reduced pressure. This wasadded dropwise with vigorous stirring to 250 ml of 12N ammoniumhydroxide while cooling to 0° C. in a salt/ice bath. When the additionwas complete the mixture was allowed to warm to ambient temperature andstir for an additional two hours. The solid that formed was collected byfiltration, dried under vacuum, and recrystallized from hexane to givetwo products. The first precipitated from hexane at room temperature togive 14.2 g of the desired 6-fluoro-2-trifluoromethylbenzamide whichmelts at 165°-6° C. and the remainder precipitated when the hexane wasremoved under reduced pressure to give 4.5 g of the2-fluoro-4-trifluoromethylbenzamide, which melts at 143°-4° C. The totalyield was 18.7 g which is 84 percent of theory.

Analysis:

Calculated for C₈ H₅ F₄ NO₂ : C, 43.06; H, 2.26; N, 6.28.

Found: C, 43.41; H, 2.13; N, 6.07.

EXAMPLE 115 Preparation of 2,6-difluoro-3-methylaniline

Sodium hydroxide (5.6 g, 0.14 mol) was dissolved in 50 ml of water andthen cooled to 0° C. in a salt/ice bath. Bromine (9.60 g, 60.0 mmoles)was slowly added to this solution and allowed to stir at 0° C. for 15minutes. To this solution was added in portions with rapid stirring2,6-difluoro-3-methylbenzamide (7.0 g, 37.0 mmol) keeping thetemperature below 5° C. The mixture was stirred at 0° C. for three hoursand then heated to reflux for two hours. It was then allowed to cool toambient temperature and was extracted with methylene chloride (2×100ml). The organic phases were combined and dried over magnesium sulfate.The solvent was removed by evaporation under reduced pressure and theresulting amber liquid distilled to give the title compound a clear,colorless oil having a b.p. of 107° C. at 15 mm Hg and amounting to 2.1g (36 percent of theory).

Analysis:

Calculated for C₇ H₇ F₂ NO: C, 52.84; H, 4.43; N, 8.80

Found: C, 52.59; H, 4.73; N, 8.97

EXAMPLE 116 Preparation of 6-trifluoromethoxy-2-trifluoromethylaniline

Sodium hydroxide (20.0 g, 0.50 mole) was dissolved in 150 ml of waterand the solution cooled to 0° C. in a salt/ice bath. Bromine (11.3 g,70.7 mmoles) was slowly added to this solution and allowed to stir at 0°C. for 15 minutes. To this solution was added in portions with rapidstirring 6-trifluoromethoxy-2-trifluoromethylbenzamide (7.0 g, 37.0mmoles) keeping the temperature below 5° C. The mixture was stirred at0° C. for five hours and then heated to reflux for 18 hours. It was thenallowed to cool to ambient temperature and was extracted with ether(2×100 ml). The organic phases were combined and dried over magnesiumsulfate. The solvent was removed by evaporation under reduced pressureand the resulting amber liquid distilled to give the title compound aclear, colorless oil having a b.p. of 152°-153° C. at 760 mm Hg andamounting to 8.2 g (47 percent of theory).

Analysis:

Calculated for C₈ H₅ F₆ NO: C, 39.20; H, 2.06; N, 5.72;

Found: C, 38.76; H, 1.99; N, 5.69

EXAMPLE 117 Preparation of 2-fluoro-6-methylthioaniline

A mixture of N-(t-butoxycarbonyl)-2-fluoroaniline (5.0 g, 24 mmoles) inanhydrous tetrahydrofuran (50 ml) was cooled to -78° C. under a nitrogenatmosphere. To this solution was added t-butyl lithium (2.0M, 57.6mmoles, 28.8 ml) at such a rate that the temperature did not exceed -65°C. When the addition was complete, the mixture was stirred at -78° C.for an additional 15 minutes and at -20° C. for 2.5 hours. To thisreaction mixture was added dimethyl disulfide (2.82 g, 30 mmoles) in 10ml of anhydrous tetrahydrofuran while maintaining the temperature at-20° C. for an additional hour. The mixture was allowed to warm toambient temperature and then 25 ml of 1N sodium hydroxide was added. Themixture obtained was extracted with diethyl ether (2×100 ml). Theorganic phase was separated and dried over magnesium sulfate and thenthe solvent was removed by evaporation under reduced pressure to obtaina tan solid. This was hydrolized in dilute hydrochloric acid (6N, 200ml) by heating to reflux for three hours. The resulting solution wasextracted with diethyl ether and the aqueous layer was neutralized withsodium hydroxide (6N, 200 ml), and extracted with methylene chloride,dried over magnesium sulfate and the solvent removed by evaporationunder reduced pressure to obtain an amber oil. This was distilled togive 3.2 g (85% of theory) of the title compound, having a b.p. of62°-65° C. at 0.2 mm Hg.

Analysis:

Calculated for C₇ H₈ FNS: C, 58.48; H, 5.13; N, 8.91.

Found: C, 53.84; H, 5.55; N, 8.73.

Representative compounds prepared employing the above general proceduresare tabulated in the following Tables I through LII.

    TABLE I      ##STR36##       Compound R.sup.1 R.sup.2 R.sup.3 R.sup.4 R.sup.5 Melting Point     Elemental Analysis              Analysis C H N Cl S       1 CF.sub.3 H H H OCH.sub.2 CF.sub.3 247-249° C. Calcd. for     C.sub.16 H.sub.13 F.sub.6 N.sub.5 O.sub.2 S: 40.9 2.79 14.92     Found: 39.9 2.78 14.75 2 CH.sub.3 H H H H 222-224° C. Calcd. for     C.sub.14 H.sub.15 N.sub.5 O.sub.2 S: 52.99 4.76 22.06        Found:     52.75 4.7922.25 3 OH H H H H >150° C. (decomp.) Calcd. for     C.sub.13 H.sub.13 N.sub.5 O.sub.3 S: 48.90 4.10 21.92        Found:     48.45 4.15 21.77 4 OCH.sub.3 H H H H 208°-210.5° C. Calcd.     for C.sub.14 H.sub.15 N.sub.5 O.sub.3 S: 50.44 5.54 21.00        Found:     50.17 4.54 21.12 5 NHCH.sub.3 H H H H 227°-228° C. Calcd.     for C.sub.14 H.sub.16 N.sub.6 O.sub.2 S: 50.59 4.85 25.28        Found:     49.70 4.87 25.12 6 I H H H H 189°-192° C. Calcd. for     C.sub.13 H.sub.12 IN.sub.5 O.sub.2 S: 36.38 2.82 16.31        Found:     36.61 2.81 16.15 7 Cl H H H H 188°-189.5° C. Calcd. for     C.sub.13 H.sub.12 CIN.sub.5 O.sub.2 S: 46.23 3.58 20.73 10.50 9.49      Found: 46.09 3.58 20.89 10.34 9.37 8 F H H H H 189°-190°     C. Calcd. for C.sub.13 H.sub.12 FN.sub.5 O.sub.2 S: 48.59 3.76 21.79     9.98        Found: 48.79 3.74 21.88 9.86 9 SCH.sub.3 H H H H 142°-     144° C. Calcd. for C.sub.14 H.sub.15 N.sub.5 O.sub.2 S.sub.2 :     48.13 4.33 20.04        Found 47.99 4.28 20.40 10 COOCH.sub.3 H H H H     169.5-170° C. Calcd. for C.sub.15 H.sub.15 N.sub.5 O.sub.4 S:     49.86 4.18 19.38 8.87        Found: 49.68 4.13 19.35 8.69  11 COOH H H H     H 247°-248° C. Calcd. for C.sub.14 H.sub.13 N.sub.5     O.sub.4 S: 48.41 3.77 20.16 9.23        Found: 47.87 3.66 20.27 8.87 12     NO.sub.2 H H H H 140° C. Calcd. for C.sub.13 H.sub.12 N.sub.6     O.sub.4 S: 44.83 3.47  24.13 9.21       Found: 44.91 3.48 24.11 9.11 13     CF.sub.3 H H H H 198.5-200.5° C. Calcd. for C.sub.14 H.sub.12     F.sub.3 N.sub. 5 O.sub.2 S: 45.28 3.26 18.86 8.63        Found: 45.39     3.16 18.74 8.87 14 CN H H H H 237.5-239° C. Exact mass calcd for     C.sub.14 H.sub.12 N.sub.6 O.sub.2 S: 328.0742        Found: 328.0748        Analysis C H N Cl S       15 SO.sub.2 nMe.sub.2 H H H H 91° C. Calcd. for C.sub.15     H.sub.18 N.sub.6 O.sub.4 S.sub.2 : 43.89 4.42 20.47 15.62        44.25     4.37 20.21 15.23 16 SO.sub.2 N(Me)Et H H H H 80° C.  Calcd. for     C.sub.16 H.sub.20 N.sub.6 O.sub.4 S.sub.2 : 45.27 4.75 19.80 15.11      Found: 45.07 4.64 19.60 14.77 17 H Cl H H H 231°-232.5°     C. Exact mass calcd. for C.sub.13 H.sub.12 CIN.sub.5 O.sub.2 S: 337.0400            Found: 337.0415 18 H H Cl H H 237°-239° C. Exact     mass calcd. for C.sub.13 H.sub.12 CIN.sub.5 O.sub.2 S: 337.0400     Found: 337.0411        Analysis C H N Cl S       19 Cl Cl H H H 214.5-216.5° C. Calcd. for C.sub.13 H.sub.11     Cl.sub.2 N.sub.5 O.sub.2 S: 41.95 2.98 18.81 19.05 8.61        Found:     42.02 3.03 18.99 18.24 8.30 20 Cl H Cl H H 176°-177.5° C.     Calcd. for C.sub.13 H.sub.11 Cl.sub.2 N.sub.5 O.sub.2 S: 41.95 2.98     18.81 19.05 8.61        Found: 42.24 2.94 18.90 18.83 8.82 21 Cl H H Cl     H 250°-253° C. Exact mass calcd. for C.sub.13 H.sub.11     Cl.sub.2 N.sub.5 O.sub.2 S: 371.0010        Found: 370.9997     Analysis C H N Cl S       22 Cl H H H Cl 260.5-262.5° C. Calcd. for C.sub.13 H.sub.11     Cl.sub.2 N.sub.5 O.sub.2 S: 41.95 2.98 18.81 19.05 8.61        Found:     42.12 2.94 19.01 18.89 8.57 23 H Cl Cl H H 240°-242° C.     Calcd. for C.sub.13 H.sub.11 Cl.sub.2 N.sub.5 O.sub.2 S: 41.95 2.98     18.81 19.05 8.61        Found: 42.32 2.87 18.82 18.65 8.42 24 H Cl H Cl     H 273.5-275.5° C. Calcd. for C.sub.13 H.sub.11 Cl.sub.2      N.sub.N.sub.5 O.sub.2 S: 41.95 2.98 18.81 19.05 8.61        Found:     42.30 2.89 18.42 18.85 8.49 25 F H H H F 229.5-231° C. Exact mass     calcd. for C.sub.13 H.sub.11 F.sub.2 N.sub.5 O.sub.2 S: 3339.0630     Found: 339.0602        Analysis C H N Cl S       26 COOMe H H H F 181.5-183.5° C. Calcd. for C.sub.15 H.sub.14     Fn.sub.5 O.sub.4 S: 47.49 3.72 18.46 8.45        Found: 47.65 3.60 18.19     8.35 27 COOH H H H F 228.5-230° C. Calcd. for C.sub.14 H.sub.12     FN.sub.5 O.sub.4 S: 46.03 3.31 19.17 8.78        Found: 45.56 3.26 19.05     8.50 28 SO.sub.2 NMe.sub.2 H H CF.sub.3 H 174.5-176.5° C. Calcd.     for C.sub.16 H.sub.17 F.sub.3 N.sub.6 O.sub.4 S.sub.2 : 40.16 3.58 17.56     13.40        Found: 40.16 3.49 17.39 13.17 29 F H F H H 233°-224.5     ° C. Calcd. for C.sub.13 H.sub.11 F.sub.2 N.sub.5 O.sub.2 S:     46.02 3.27 20.63        Found: 46.19 3.37 20.59 30 Cl H F H H 203°     -205°  C. Calcd. for C.sub.13pl H.sub.11 ClFN.sub.5 O.sub.2 S:     43.89 3.12 19.68        Found: 44.02 3.12 19.89 31 Cl H H H CH.sub.3     230°-231.5° C. Calcd. for C.sub.14 H.sub.14 ClN.sub.5     O.sub.2 S: 47.82 3.98 19.07       (decomp.) Found: 47.87 4.06 19.66 32     Ch.sub.3 H H H CH.sub.3 263°-266° C. Calcd. for C.sub.15     H.sub.17 N.sub.5 O.sub.2 S: 54.31 5.23 21.23       (decomp.) Found:     53.59 5.07 20.65 33 CH.sub.2 CH.sub.3 H H H CH.sub.2      CH.sub.3 248-249.5° C. Calcd. for C.sub.17 H.sub.21 N.sub.5     N.sub.5 O.sub.2 S: 56.83 5.84 19.48       (decomp.) Found: 57.06 5.98     19.40 34 CF.sub.3 H Cl H H 189°-193° C. Calcd. for     C.sub.14 H.sub.11 ClF.sub.3 N.sub.5 O.sub.2 S: 41.41 2.71 17.25     (decomp.) Found: 41.78 2.73 17.23 35 Cl H Cl H Cl >200° C. Calcd.     for C.sub.13 H.sub.10 Cl.sub.3 N.sub.5 O.sub.2 S: 38.40 2.48 17.22     (decomp.) Found: 38.36 2.48 17.14 36 COO.sub.-iPr H H H H 130°-132     ° C. Calcd. for C.sub.17 H.sub.19 N.sub.5 O.sub.4 S: 52.43 4.92     17.98        Found: 51.83 4.77 17.70 37 CONH.sub.2 H H H H 258°-26     0° C. Calcd. for C.sub.14 H.sub.14 N.sub.6 O.sub.3 S: 48.55 4.07     24.26        Found: 48.58 4.00 24.01 38 Br H H H Br 285°-287.degre     e. C. Calcd. for C.sub.13 H.sub.11 Br.sub.2 N.sub.5 O.sub.2 S: 33.86     2.40 15.18        Found: 33.92 2.42 15.41 39 Br H H H Cl >230° C.     Calcd. for C.sub.13 H.sub.11 BrClN.sub.5 O.sub.2 S:: 37.47 2.66 16.80        (decomp.) Found: 37.50 2.64 16.87 40 Br H Cl H H 177°-179.degre     e. C. Calcd. for C.sub.13 H.sub.11 BrClN.sub.5 O.sub.2 S: 37.47 2.66     16.80        Found: 37.45 2.67 16.64 41 Br H H H H 188°-190.degree     . C. Calcd. for C.sub.13 H.sub.12 BrN.sub.5 O.sub.2 S: 40.85 3.16 18.32           Found: 41.09 3.12 18.19 42 CONMe.sub.2 H H H H 193°-194.degr     ee. C. Calcd. for C.sub.16 H.sub.18 N.sub.6 O.sub.3 S: 51.33 4.85 22.44           Found: 51.08 4.65 22.12 43 CONMe.sub.2 H Cl H H 194°-195.deg     ree.C. Calcd. for C.sub.16 H.sub.17 ClN.sub.6 O.sub.3 S: 47.00 4.19     20.55        Found: 47.16 4.07 20.50 44 Cl H F H Cl 271°-273.degre     e. C. Calcd. for C.sub.13 H.sub.10 Cl.sub.2 FN.sub.5 O.sub.2 S: 40.02     2.58 17.94       (decomp.) Found: 40.13 2.65 18.04 45 SO.sub.2 Me H H H     H 181°-183° C. Calcd. for C.sub.14 H.sub.15 N.sub.5     O.sub.4 S.sub.2 : 44.09 3.96 18.35        Found: 43.64 3.84 18.16 46 Cl     Me H H Cl 280° C. Calcd. for C.sub.14 H.sub.13 Cl.sub.2 N.sub.5     O.sub.2 S: 43.54 3.39 18.13       (decomp.) Found: 43.45 3.37 18.15 47     Cl H Me H Cl 245°-248° C. Calcd. for C.sub.14 H.sub.13     Cl.sub.2 N.sub.5 O.sub.2 S: 43.54 3.39 18.13        Found: 43.57 3.37     18.21 48 Cl H Me H H 229°-231° C. Calcd. for C.sub.14     H.sub.14 ClN.sub.5 O.sub.2 S: 48.00 4.01 19.90        Found: 48.01 3.97     20.05 49 NO.sub.2 H H H CH.sub.3 244°-246° C. Exact mass     calcd. for C.sub.14 H.sub.14 N.sub.6 O.sub.4 S: 362.0799        Found:     362.0807        Analysis  C H N Cl S       50 COOMe H H H CH.sub.3 CAlcd. for C.sub.16 H.sub.17 N.sub.5 O.sub.4     S: 51.19 4.57 18.65        Found: 51.22 4.58 18.46 51 COO.sub.-i-Pr H H     H F 167°-168° C. Calcd. for C.sub.17 H.sub.18 FN.sub.5     O.sub.4 S: 50.12 4.45 17.18        Found: 50.09 4.39 17.28 52 I H H     CF.sub.3 H 221.5°-224° C. Calcd. for C.sub.14 H.sub.10     ClF.sub.3 N.sub.5 O.sub.2 S: 41.43 2.71 17.24        Found: 41.73 2.74     17.08 53 I H H H Cl >258° C. Calcd. for C.sub.13 H.sub.11     ClIN.sub.5 O.sub.2 S: 33/68 2.39 15.10       (decomp.) Found: 33.66 2.38     15.03 54* Cl H H H F 223°-225.5° C. Calcd. for C.sub.13     H.sub.11 ClFN.sub.5 O.sub.2 S: 43.89 3.12 19.68       (decomp.) Found:     43.20 2.89 19.41 55 SCF.sub.3 H H H H 175-178° C. Calcd. for     C.sub.14 H.sub.12 F.sub.3 N.sub.5 O.sub.2 S.sub.2 : 41.68 2.97 17.35        Found: 40.84 2.95 16.61 56 COO.sub.-t-Bu H H H F 151-153° C.     Cald. for C.sub.18 H.sub.20 FN.sub.5 O.sub.4 S: 51.30 4.78 16.61     (decomp.) Found: 50.90 4.69 16.49 57 SO.sub.2      CF.sub.3 H H H H 68-70° C. Calcd. for C.sub.14 H.sub.12 F.sub.3     N.sub.5 O.sub.4 S.sub.2 : 38.62 2.75 16.09        Found: 39.10 2.71     15.87 58 Br H H H CH.sub.3 225-228° C. Calcd. for C.sub.14     H.sub.14 BrN.sub.5 O.sub.2 S: 42.44 3.56 17.67        Found: 42.56 3.55     17.66 59 SCF.sub.2 CF.sub.2 H H H H H 162.5-164° C. Calcd. for     C.sub.15 H.sub.13 F.sub.4 N.sub.5 O.sub.2 S.sub.2 : 41.38 3.01 16.08     14.73        Found: 41.54 2.88 16.06 14.57 60 SOCF.sub.2 CF.sub.2 H H H     H H 223-224° C. Calcd. for C.sub.15 H.sub.13 F.sub.4 N.sub.5     O.sub.3 S.sub.2 : 39.91 2.90 15.51 14.21        Found: 39.88 2.83 15.37     14.15 61 CONH.sub.2 H H H CH.sub.3 231-232° C. Calcd. for     C.sub.15 N.sub.16 N.sub.6 O.sub.3 S. H.sub.2 O: 47.61 4.80 22.20     Found: 47.74 4.71 22.04 62 CONMe.sub.2 H H H CH.sub.3 225-257° C.     Calcd: for C.sub.17-16N6 O.sub.3 S: 52.57 5.19 21.63        Found: 52.19     5.15 21.39 63 Cl H H H Ph 256-260° C. Calcd. for C.sub.19     H.sub.16 ClN.sub.5 O.sub.2 S: 55.14 3.90 16.92       (decomp.) Found:     54.68 3.89 16.96 64 Coo.sub.-i-Pr H H H CH.sub.3 178-179° C.     Calcd. for C.sub.18 H.sub.21 N.sub.5 O.sub.4 S: 53.59 5.25 17.35     Found: 53.32 5.18 17.15 65 CH.sub.3 Cl H H CH.sub.3 279-282° C.     Calcd. for C.sub.15 H.sub.16 C'N.sub.5 O.sub.2 S: 49.25 4.41 19.14     (decomp.) Found: 49.05 4.38 19.00 66 SCH.sub.2 CHCH.sub.2 H H H H     113-114° C. Calcd. for C.sub.16 H.sub.17 N.sub.5 O.sub.2 S.sub.2     : 51.17 4.56 18.65        Found: 51.29 4.63 18.94 67 SCH.sub.2 CH.sub.2     CH.sub.3 H H H H 124° Calcd. for C.sub.16 H.sub.19 N.sub.5     O.sub.2 S.sub.2 : 50.90 5.07 18.55       (decomp.) Found: 50.41 4.76     18.79 68 CH.sub.3 Cl H H H 223-225° C. Calcd. for C.sub.14     H.sub.14 ClN.sub.5 O.sub.2 S: 47.79 4.01 19.91        Found: 47.52 4.31     19.84 69 SCH.sub.3 H H H Cl 171-172° C Calcd. for C.sub.14     H.sub.14 ClN.sub.5 O.sub.2 S.sub.2 : 43.80 3.68 18.24        Found:     44.00 3.74 17.96 70 SCH.sub.3 H H H CH.sub.3 200-202° C. Calcd.     for C.sub.15 H.sub.17 N.sub.5 O.sub.2 S.sub.2 : 49.56 4.71 19.27     Found: 49.78 4.49 18.68 71 CHNOH H H H OCH.sub.3 244-246° C.     Calcd. for C.sub.15 H.sub.16 N.sub.6 O.sub.4 S: 47.86 4.29 22.33     Found: 47.47 4.03 23.36 72 CO.sub.2 CH.sub.2 CH.sub.2 OEt H H H CH.sub.3     78-80° C. Calcd. for C.sub.19 H.sub.23 N.sub.5 O.sub.5 S: 52.65     5.35 16.16        Found: 51.68 5.11 16.37 73 CO.sub.2 CH.sub.2 CH.sub.2     NMe.sub.2 H H H CH.sub.3 207-208° C. Calcd. for C.sub.19 H.sub.24     N.sub.6 O.sub.4 S: 52.76 5.59 19.43        Found: 52.06 5.48 19.18 74 Cl     Cl H H CH.sub.3 287-289° C. Calcd. for C.sub.14 H.sub.13 Cl.sub.2     N.sub.5 O.sub.2 S: 43.54 3.39 18.13       (decomp.) Found: 43.74 3.46     18.48 75 COOPh H H H CH.sub. 3 159.5-160.5° C. Calcd. for     C.sub.21 H.sub.19 N.sub.5 O.sub.4 S: 57.66 4.38 16.01        Found:     57.17 4.46 15.74 76 CO.sub.2 CH.sub.2      CHCH.sub.2 H H H CH.sub.3 158-158.5° C. Calcd. for C.sub.18     H.sub.19 N.sub.5 O.sub.4 S: 53.86 4.77 17.44        Found: 53.47 4.63     17.54      77     ##STR37##      H H H CH.sub.3 165.5-166° C Calcd. for C.sub.21 H.sub.20 N.sub.6     O.sub.4 S:Found: 55.7455.82 4.464.43 18.5718.32  78 CO.sub.2      NC(CH.sub.3).sub.2) H H H CH.sub.3 91-94° C. Calcd. for C.sub.18     H.sub.20 N.sub.6 O.sub.4 S: 51.91 4.84 10.18        Found: 51.51 4.68     19.70 79 CHNOCH.sub.3 H H H OCH.sub.3 227-229° C. Calcd. for     C.sub.16 H.sub.18 N.sub.6 O.sub.4 S: 49.22 4.65 21.53        Found:     49.00 4.63 21.24 80 S.sub.-t-Bu H H H H 144-146° C. Calcd. for     C.sub.17 H.sub.21 N.sub.5 O.sub.2 S.sub.2 : 52.15 5.41 17.89     Found: 52.31 5.34 17.92 81 Cl H H COOMe H 175-177° C. Calcd. for     C.sub.15 H.sub.14 ClN.sub.5 O.sub.4 S: 45.52 3.57 17.69        Found:     45.42 3.45 17.66 82 Cl COOMe H H Cl 217-221° C. Calcd. for     C.sub.15 H.sub.13 Cl.sub.2 N.sub.5 O.sub.4 S: 41.87 3.05 16.27     (decomp.) Found: 41.96 3.10 16.22 83 Cl CF.sub.3 H H Cl 286-290°     C. Calcd. for C.sub.14 H.sub.10 Cl.sub.2 F.sub.3 N.sub.5 O.sub.2 S:     38.20 2.29 15.90       (decomp.) Found: 38.36 2.29 16.63 84 Cl H H     CO.sub.2.sub.-i-Pr H 182-185° C. Calcd. for C.sub.17 H.sub.18     ClN.sub.5 O.sub.4 S: 48.17 4.28 16.52        Found: 48.31 4.17 16.51 85     NO.sub.2 H H CH.sub.3 CH.sub.3 254-257° C. Calcd. for C.sub.15     H.sub.16 N.sub.6 O.sub.4 S: 47.87 4.29 22.32       (decomp.) Found:     47.52 4.01 22.47 86 Br COOMe H H CH.sub.3 229-231° C. Calcd. for     C.sub.16 H.sub.16 BrN.sub.5 O.sub.4 S: 42.30 3.55 15.41        Found:     42.29 3.45 15.68 87 Br COO.sub.-i-Pr H H CH.sub.3 208-211° C.     Calcd. for C.sub.18 H.sub.20 BrN.sub.5 O.sub.4 S: 44.82 4.18 14.51      Found: 45.09 4.11 14.39 88 Br COO.sub.-t-Bu H H CH.sub.3 181-183°      C. Calcd. for C.sub.19 H.sub.22 BrN.sub.5 O.sub.4 S: 45.98 4.47 14.10         (decomp.) Found: 45.61 4.17 13.84 89 COMe H H H H 166-168° C.     Calcd. for C.sub.15 H.sub.15 N.sub.5 O.sub.3 S: 52.16 4.38 20.28     Found: 52.07 4.19 20.37 90 F F H F F 148-149° C. Calcd. for     C.sub.13 H.sub.9 F.sub.4 N.sub.5 O.sub.2 S: 41.60 2.42 18.66     (decomp.) Found: 42.25 2.50 18.52 91 CH.sub.2 OCH.sub.3 H H H Cl     201-202° C. Calcd. for C.sub.15 H.sub.16 ClN.sub.5 O.sub.3 S:     47.19 4.22 18.33        Found: 47.07 4.16 18.87 92 CH.sub.2 OCH.sub.2 Ph     H H H Cl 169-171° C. Calcd. for c.sub.21 H.sub.20 cLN.sub.5     O.sub.3 S: 55.08 4.40 15.29        Found: 54.99 4.38 15.30 93 CH.sub.2     OH H H H Cl 208-209° C. Calcd. for C.sub.14 H.sub.14 ClN.sub.5     O.sub.3 S.H.sub.2 O: 43.60 4.18 18.14        Found: 43.50 3.75 18.43 94     CH.sub.2 OAc H H H Cl 214-217° C. Calcd. for C.sub.16 H.sub.16     ClN.sub.5 O.sub.4 S: 46.89 3.94 17.08        Found: 46.60 3.80 17.73 95     COPh H H H H 169-170° C. Calcd. for C.sub. 20 H.sub.17 N.sub.5     O.sub.3 S: 58.95 4.21 17.19        Found: 58.67 4.14 17.51 96 SO.sub.2     Ph H H H H 152-154° C. Calcd. for C.sub.19 H.sub.17 N.sub.5     O.sub.4 S.sub.2 : 51.46 3.86 15.79        Found: 51.31 3.81 15.81  97      ##STR38##      H H H H 176-177° C. Calcd. for C.sub.20 H.sub.15 ClF.sub.3     N.sub.5 O.sub.3 S:Found: 48.2448.11 3.033.09 14.0614.49      98     ##STR39##      H H H F 211-213° C. Calcd. for C.sub.20 H.sub.14 ClF.sub.4     N.sub.5 O.sub.3 S:Found: 46.5646.02 2.742.74 13.5713.40      99     ##STR40##      H H H H 178-180° C. Calcd. for C.sub.19 H.sub.14 ClF.sub.3     N.sub.6 O.sub.3 S:Found: 45.7445.66 2.842.81 16.8517.02  100 Cl H H COOH     H 276-278° C. Calcd. for C.sub.14 H.sub.12 ClN.sub.5 O.sub.4 S:     44.04 3.17 18.34        Found: 44.06 3.24 18.37 101 Br COOH H H CH.sub.3     290° C. Calcd. for C.sub.15 H.sub.14 BrN.sub.5 O.sub.4 S: 40.92     3.21 15.90       (decomp.) Found: 40.51 3.11 16.01 102 CO.sub.2 Me H H     CO.sub.2 Me H 191-194° C. Calcd. for C.sub.17 H.sub.17 N.sub.5     O.sub.6 S: 48.68 4.09 16.70        Found: 48.47 4.01 16.32 103 COOH H H     H CH.sub.3 268-271° C. Calcd. for C.sub.15 H.sub.15 N.sub.5     O.sub.4 S.1/2H.sub.2 O: 48.64 4.35 18.90        Found: 48.88 4.00 19.20     104 CF.sub.3 H H H OCH.sub.3 246-249° C. Calcd. for C.sub.15     H.sub.14 F.sub. 3 N.sub.5 O.sub.3 S: 44.91 3.49 17.47        Found:     44.77 3.61 17.94     *This compound contains 15% where R.sup.1 = R.sup.3 = Cl and R.sup.5 = F.

                                      TABLE II                                    __________________________________________________________________________     ##STR41##                                                                                                  Elemental Analysis                              Compound                                                                            R.sup.1 R.sup.2                                                                         R.sup.3                                                                         R.sup.4                                                                         R.sup.5                                                                         Melting Point                                                                         Analysis      C  H  N                           __________________________________________________________________________    105   NO.sub.2                                                                              H H H H 110°-112° C.                                                            Calcd. for C.sub.15 H.sub.14 N.sub.6                                          O.sub.4 S:    48.11                                                                            3.73                                                                             22.43                                             (decomp.)                                                                             Found:        46.96                                                                            3.54                                                                             21.62                       106   CF.sub.3                                                                              H H H H ca. 200° C.                                                                    Calcd. for C.sub.16 H.sub.14 F.sub.3                                          N.sub.5 O.sub.2 S:                                                                          48.35                                                                            3.52                                                                             17.61                                                     Found:        48.08                                                                            3.40                                                                             17.40                       107   SO.sub.2 NMe.sub.2                                                                    H H H H 188°-189° C.                                                            Calcd. for C.sub.17 H.sub.20 N.sub.6                                          O.sub.4 S.sub.2 :                                                                           46.78                                                                            4.58                                                                             19.24                                             (decomp.)                                                                             Found:        46.04                                                                            4.85                                                                             18.90                       108   Cl      H H H H 264°-266° C.                                                            Calcd. for C.sub.15 H.sub.13 Cl.sub.2                                         N.sub.5 O.sub.2 S:                                                                          45.24                                                                            3.29                                                                             17.58                                                     Found:        45.47                                                                            3.18                                                                             17.41                       109   COOMe   H H H H 180°-182° C.                                                            Calcd. for C.sub.17 H.sub.17 N.sub.5                                          O.sub.4 S:    52.71                                                                            4.42                                                                             18.07                                             (decomp.)                                                                             Found:        52.19                                                                            4.28                                                                             18.12                       110   COO .sub.-i-Pr                                                                        H H H H 170°-172° C.                                                            Calcd. for C.sub.19 H.sub.21 N.sub.5                                          O.sub.4 S:    54.93                                                                            5.10                                                                             16.85                                                     Found:        54.82                                                                            5.01                                                                             16.59                       __________________________________________________________________________

                                      TABLE III                                   __________________________________________________________________________     ##STR42##                                                                                           Elemental Analysis                                     Cmpd.                                                                             R.sup.1                                                                          R.sup.2                                                                         R.sup.3                                                                         R.sup.4                                                                         R.sup.5                                                                          Melting Point                                                                        Analysis      C  H  N  S  Cl                           __________________________________________________________________________    111 Cl H H H Cl 296-298° C.                                                                   Calcd. for C.sub.14 H.sub.13 Cl.sub.2 N.sub.5                                 O.sub.2 S:    43.53                                                                            3.39                                                                             18.13                                                                            8.30                                                                             18.36                                               Found:        44.07                                                                            3.42                                                                             18.16                                                                            7.89                                                                             17.73                        112 CF.sub.3                                                                         H H H H  197-199° C.                                                                   Calcd. for C.sub.15 H.sub.14 F.sub.3 N.sub.5                                  O.sub.2 S:    46.75                                                                            3.66                                                                             18.17                                                                            8.32                                                   Found:        46.54                                                                            3.52                                                                             18.30                                                                            8.59                            113 Cl H H H CH.sub.3                                                                         306-309° C.                                                                   Calcd. for C.sub.15 H.sub.16 ClN.sub.5 O.sub.2                                              49.25                                                                            4.41                                                                             19.14                                                                            8.76                                                                             9.69                                                Found:        48.70                                                                            4.29                                                                             19.23                                                                            8.82                                                                             9.57                         __________________________________________________________________________

                                      TABLE IV                                    __________________________________________________________________________     ##STR43##                                                                                                    Elemental Analysis                            Cmpd.                                                                             R.sup.1                                                                              R.sup.2                                                                           R.sup.3                                                                          R.sup.4                                                                          R.sup.5                                                                           Melting Point                                                                        Analysis      C  H  N                         __________________________________________________________________________    114 Cl     H   H  H  Cl  246-248° C.                                                                   Calcd. for C.sub.11 H.sub.6 Cl.sub.3                                          N.sub.5 O.sub.2 S:                                                                          34.89                                                                            1.60                                                                             18.50                                                     Found:        35.02                                                                            1.65                                                                             18.09                     115 SMe    H   H  H  H   159-162° C.                                                                   Calcd. for C.sub.12 H.sub.10 ClN.sub.5                                        O.sub.2 S.sub.2 :                                                                           40.50                                                                            2.81                                                                             19.60                                                     Found:        40.39                                                                            2.95                                                                             19.90                     116 F      H   H  H  Cl  254- 257° C.                                                                  Calcd. for C.sub.11 H.sub.6 Cl.sub.2                                          FN.sub.5 O.sub.2 S:                                                                         36.48                                                                            1.67                                                                             19.34                                                     Found:        37.21                                                                            1.91                                                                             18.74                     117 F      H   H  H  F   224-226° C.                                                                   Calcd. for C.sub.11 H.sub.6 ClF.sub.2                                         N.sub.5 O.sub.2 S:                                                                          38.21                                                                            1.75                                                                             20.26                                                     Found:        38.32                                                                            1.44                                                                             20.18                     118 CF.sub.3                                                                             H   H  H  H   179-180° C.                                                                   Calcd. for C.sub.12 H.sub.7 ClF.sub.3                                         N.sub.5 O.sub.2 S:                                                                          38.15                                                                            1.87                                                                             18.54                                                     Found:        38.19                                                                            1.59                                                                             18.00                     119 Cl     H   H  H  CH.sub.3                                                                          223-226° C.                                                                   Calcd. for C.sub.12 H.sub.9 Cl.sub.2                                          N.sub.5 O.sub.2 S:                                                                          40.23                                                                            2.53                                                                             19.55                                                     Found:        40.44                                                                            2.06                                                                             19.27                     120 CF.sub.3                                                                             H   H  H  OCH.sub.3                                                                         205-206° C.                                                                   Calcd. for C.sub.13 H.sub.9 ClF.sub.3                                         N.sub.5 O.sub.3 S:                                                                          38.29                                                                            2.22                                                                             17.18                                                     Found:        38.03                                                                            2.35                                                                             17.39                     121 Cl     H   H  H  H   188-189° C.                                                                   Calcd. for C.sub.11 H.sub.7 Cl.sub.2                                          N.sub.5 O.sub.2 S:                                                                          38.39                                                                            2.05                                                                             20.35                                                     Found:        38.26                                                                            1.84                                                                             19.98                     122 COOMe  H   H  H  H   187-188° C.                                                                   Calcd. for C.sub.13 H.sub.10 ClN.sub.5                                        O.sub.4 S:    42.46                                                                            2.74                                                                             19.04                                                     Found:        42.54                                                                            2.79                                                                             19.13                     123 SO.sub.2 NMe.sub.2                                                                   H   H  H  H   164-165° C.                                                                   Calcd. for C.sub.13 H.sub.13 ClN.sub.6                                        O.sub.4 S.sub.2 :                                                                           37.46                                                                            3.14                                                                             20.16                                                     Found:        37.42                                                                            3.21                                                                             20.25                     124 H      Br  H  H  H   245-247° C.                                                                   Calcd. for C.sub.11 H.sub.7 BrClN.sub.5                                       O.sub.2 S:    34.00                                                                            1.82                                                                             18.02                                                     Found:        34.49                                                                            1.90                                                                             18.31                     125 H      H   CF.sub.3                                                                         H  H   239-241° C.                                                                   Calcd. for C.sub.12 H.sub.7 F.sub.3                                           ClN.sub.5 O.sub.2 S:                                                                        38.16                                                                            1.87                                                                             18.54                                                     Found:        38.54                                                                            1.83                                                                             18.83                     126 CONMe.sub.2                                                                          H   H  H  H   162-163° C.                                                                   Calcd. for C.sub.14 H.sub.13 ClN.sub.6                                        O.sub.3 S:    44.16                                                                            3.44                                                                             22.07                                                     Found:        44.57                                                                            3.47                                                                             22.43                     127 COO .sub.-iPr                                                                        H   H  H  H   158-160° C.                                                                   Calcd. for C.sub.15 H.sub.14 ClN.sub.5                                        O.sub.4 S:    45.52                                                                            3.57                                                                             17.69                                                     Found:        45.54                                                                            3.49                                                                             17.93                     128 Cl     H   H  H  Ph  243-245° C.                                                                   Calcd. for C.sub.17 H.sub.11 Cl.sub.2                                         N.sub.5 O.sub.2 S:                                                                          48.58                                                                            2.64                                                                             16.66                                                     Found:        49.24                                                                            2.62                                                                             16.65                     129 CH.sub.3                                                                             H   H  H  H   170-171° C.                                                                   Calcd. for C.sub.12 H.sub.10 ClN.sub.5                                        O.sub.2 S:    44.52                                                                            3.11                                                                             21.63                                                     Found:        44.66                                                                            3.04                                                                             21.96                     130 H      H    -n-Bu                                                                           H  H   233-235° C.                                                                   Calcd. for C.sub.15 H.sub.16 ClN.sub.5                                        O.sub.2 S:    49.25                                                                            4.41                                                                             19.14                                                     Found:        49.10                                                                            4.30                                                                             19.30                     131 H      OCH.sub.3                                                                         H  H  H   212-215° C.                                                                   Calcd. for C.sub.12 H.sub.10 ClN.sub.5                                        O.sub.3 S:    42.42                                                                            2.97                                                                             20.61                                                     Found:        42.33                                                                            2.97                                                                             20.65                     132 SO.sub.2 N(Me)Et                                                                     H   H  H  H   155-157° C.                                                                   Calcd. for C.sub.14 H.sub.15 ClN.sub.6                                        O.sub.4 S.sub.2 :                                                                           39.02                                                                            3.51                                                                             19.50                                                     Found:        39.17                                                                            3.47                                                                             19.54                     133 F      H   H  H  H   171-172° C.                                                                   Calcd. for C.sub.11 H.sub.7 ClFN.sub.5                                        O.sub.2 S:    40.32                                                                            2.15                                                                             21.37                                                     Found:        41.00                                                                            2.18                                                                             21.55                     134 H      SCH.sub.3                                                                         H  H  H   210-212° C.                                                                   Calcd. for C.sub.12 H.sub.10 ClN.sub.5                                        O.sub.2 S.sub.2 :                                                                           40.51                                                                            2.83                                                                             19.68                                                     Found:        39.29                                                                            2.77                                                                             19.70                     __________________________________________________________________________

                                      TABLE V                                     __________________________________________________________________________     ##STR44##                                                                                                Elemental Analysis                                Cmpd.                                                                             R.sup.1                                                                            R.sup.2                                                                          R.sup.3                                                                         R.sup.4                                                                         R.sup.5                                                                           Melting Point                                                                         Analysis     C  H  N                              __________________________________________________________________________    135 SCH.sub.3                                                                          H  H H H   162.5-165° C.                                                                  Calcd. for C.sub.12 H.sub.11 N.sub.5 O.sub.2                                  S.sub.2 :    44.85                                                                            3.43                                                                             21.78                                              (decomp.)                                                                             Found:       44.35                                                                            3.43                                                                             22.08                          136 CF.sub.3                                                                           H  H H H   168.5-171° C.                                                                  Calcd. for C.sub.12 H.sub.8 F.sub.3 N.sub.5                                   O.sub.2 S.sub.2 :                                                                          42.11                                                                            2.33                                                                             20.45                                              (decomp.)                                                                             Found:       41.93                                                                            2.28                                                                             19.99                          137 Cl   H  H H Cl  278- 280° C.                                                                   Calcd. for C.sub.11 H.sub.7 Cl.sub.2 N.sub.5                                  O.sub.2 S:   38.38                                                                            2.03                                                                             20.35                                                      Found:       38.28                                                                            1.70                                                                             20.75                          138 F    H  H H F   296-299° C.                                                                    Calcd. for C.sub.11 H.sub.7 F.sub.2 N.sub.5                                   O.sub.2 S:   42.46                                                                            2.25                                                                             22.52                                              (decomp.)                                                                             Found:       42.27                                                                            2.30                                                                             22.60                          139 Cl   CH.sub.3                                                                         H H Cl  252-255° C.                                                                    Calcd. for C.sub.12 H.sub.9 Cl.sub.2 N.sub.5                                  O.sub.2 S:   40.23                                                                            2.51                                                                             19.55                                              (decomp.)                                                                             Found:       40.00                                                                            2.65                                                                             19.75                          140 F    CH.sub.3                                                                         H H F   280-283° C.                                                                    Calcd. for C.sub.12 H.sub.9 F.sub.2 N.sub.5                                   O.sub.2 S:   44.32                                                                            2.77                                                                             21.55                                              (decomp.)                                                                             Found:       44.10                                                                            2.81                                                                             21.55                          141 CF.sub.3                                                                           H  H H OCH.sub.3                                                                         230-232° C.                                                                    Calcd. for C.sub.13 H.sub.10 F.sub.3 N.sub.5                                  O.sub.3 S:   41.80                                                                            2.68                                                                             18.78                                                      Found:       41.80                                                                            2.77                                                                             18.69                          __________________________________________________________________________

                                      TABLE VI                                    __________________________________________________________________________     ##STR45##                                                                    Cmpd.                                                                             R.sup.1                                                                              R.sup.2                                                                           R.sup.3                                                                          R.sup.4                                                                          R.sup.5                                                                             Melting Point                                                                         Elemental Analysis                         __________________________________________________________________________                                       Analysis      C  H   N  S                  142 SCH.sub.3                                                                            H   H  H  H     166°-169° C.                                                            Calcd. for C.sub.13 H.sub.13 N.sub.5                                          O.sub.2 S.sub.2 :                                                                           45.67                                                                            3.77                                                                              20.11                                                    Found:        47.34                                                                            3.90                                                                              19.86                 143 Cl     H   H  H  Cl    228.5°-230° C.                                                          Calcd. for C.sub.12 H.sub.9 Cl.sub.2                                          N.sub.5 O.sub.2 S:                                                                          40.24                                                                            2.51                                                                              19.54                                                    Found:        40.34                                                                            2.52                                                                              19.09                 144 Cl     H   H  H  CH.sub.3                                                                            211-215° C.                                                                    Calcd. for C.sub.13 H.sub.12 ClN.sub.5                                        O.sub.2 S:    46.19                                                                            3.55                                                                              20.72                                            (decomp.)                                                                             Found:        45.91                                                                            3.43                                                                              20.70                 145 CF.sub.3                                                                             H   H  H  H     144-145° C.                                                                    Calcd. for C.sub.13 H.sub.10 F.sub.3                                          N.sub.5 O.sub.2 S:                                                                          43.67                                                                            2.79                                                                              19.59                                                    Found:        43.67                                                                            2.74                                                                              19.52                 146 COOMe  H   H  H  CH.sub.3                                                                            184-186° C.                                                                    Calcd. for C.sub.15 H.sub.15 N.sub.5                                          O.sub.4 S:    49.84                                                                            4.15                                                                              19.38                                                    Found:        49.65                                                                            4.13                                                                              19.45                 147 Cl     CH.sub.3                                                                          H  H  Cl    140° C.                                                                        Calcd. for C.sub.12 H.sub.11 Cl.sub.2                                         N.sub.5 O.sub.2 S:                                                                          41.91                                                                            2.95                                                                              18.80                                            (decomp.)                                                                             Found:        41.92                                                                            2.83                                                                              18.45                 148 Br     H   H  H  CH.sub.3                                                                            106° C.                                                                        Calcd. for C.sub.13 H.sub.12 BrN.sub.5                                        O.sub.2 S:    40.83                                                                            3.14                                                                              18.32                                            (decomp.)                                                                             Found:        40.36                                                                            3.14                                                                              18.30                 149 SOCF.sub.2 CF.sub.2 H                                                                H   H  H  H     180° C.                                                                        Calcd. for C.sub.14 H.sub.11 F.sub.4                                          N.sub.5 O.sub.3 S.sub.2 :                                                                   38.40                                                                            2.52                                                                              16.03                                            (decomp.)                                                                             Found:        36.70                                                                            2.50                                                                              14.69                 150 SCH.sub.3                                                                            H   H  H  CH.sub.3                                                                            234° C.                                                                        Calcd. for C.sub.14 H.sub.15 N.sub.5                                          O.sub.2 S.sub.2 :                                                                           48.12                                                                            4.33                                                                              20.04                                            (decomp.)                                                                             Found:        47.89                                                                            4.17                                                                              20.31                 151 NO.sub.2                                                                             H   H  H  CH.sub.3                                                                            120° C.                                                                        Calcd. for C.sub.13 H.sub.12 N.sub.6                                          O.sub.4 S:    44.82                                                                            3.47                                                                              24.13                                            (decomp.)                                                                             Found:        45.94                                                                            3.30                                                                              23.75                 152 Br     H   H  H  Cl    230-235° C.                                                                    Calcd. for C.sub.12 H.sub.9 BrClN.sub.5                                        O.sub.2 S:   35.79                                                                            2.25                                                                              17.39                                                    Found:        35.50                                                                            2.19                                                                              17.97                 153 I      H   H  H  Cl    210-215° C.                                                                    Calcd. for C.sub.12 H.sub.9 ClIN.sub.5                                        O.sub.2 S:    32.05                                                                            2.02                                                                              15.58                                                    Found:        32.36                                                                            2.29                                                                              15.31                 154 Cl     H   H  H  Ph    233-243° C.                                                                    Calcd. for C.sub.18 H.sub.14 ClN.sub.5                                        O.sub.2 S:    54.07                                                                            3.53                                                                              17.52                                                                            8.02                                          (decomp.)                                                                             Found:        53.49                                                                            3.45                                                                              17.82                                                                            8.49               155 Cl     Cl  H  H  CH.sub.3                                                                            256-259° C.                                                                    Calcd. for C.sub.13 H.sub.11 Cl.sub.2                                         N.sub.5 O.sub.2 S:                                                                          41.95                                                                            2.98                                                                              18.81                                                                            8.61                                          (decomp.)                                                                             Found:        42.00                                                                            2.96                                                                              18.75                                                                            8.63               156 COOCH.sub.3                                                                          H   H  Cl CH.sub.3                                                                            75-80° C.                                                                      Calcd. for C.sub.15 H.sub.14 ClN.sub.5                                        O.sub.4 S:    45.52                                                                            3.57                                                                              17.69                                                                            8.10                                                  Found:        45.28                                                                            3.57                                                                              17.41                                                                            8.07               157 F      H   H  H  F     245-247° C.                                                                    Calcd. for C.sub.12 H.sub.9 F.sub.2                                           N.sub.5 O.sub.2 S:                                                                          44.30                                                                            2.79                                                                              21.53                                                    Found:        44.69                                                                            2.80                                                                              21.85                 158 F      H   H  H  Cl    243-248° C.                                                                    Calcd. for C.sub.12 H.sub.9 ClFN.sub.5                                        O.sub.2 S:    42.17                                                                            2.65                                                                              20.49                                                    Found:        42.14                                                                            2.63                                                                              20.18                 159 COOMe  H   H  H  F     159-163° C.                                                                    Calcd. for C.sub.14 H.sub.12 FN.sub.5                                         O.sub.4 S:    46.03                                                                            3.31                                                                              19.16                                                    Found:        45.56                                                                            3.08                                                                              19.25                  160                                                                              NO.sub.2                                                                             H   H  CH.sub.3                                                                         CH.sub.3                                                                            225-230° C.                                                                    Exact mass calcd. for C.sub.14                                                H.sub.14 N.sub.6 O.sub.4 S:                                                                     262.0799                                                    Found:            262.0802                                                    Analysis      C  H   N  S                  161 F      H   H  H  SCH.sub.3                                                                           190-192° C.                                                                    Calcd. for C.sub.13 H.sub.12 FN.sub.5                                         O.sub.2 S.sub.2 :                                                                           44.18                                                                            3.42                                                                              19.82                                                    Found:        44.02                                                                            3.41                                                                              19.51                 162 F      H   H  H  CH.sub.3                                                                            241° C.                                                                        Calcd. for C.sub.13 H.sub.12 FN.sub.5                                         O.sub.2 S:    48.59                                                                            3.76                                                                              21.80                                            (decomp.)                                                                             Found:        48.31                                                                            3.51                                                                              21.62                 163 F      F   H  F  F     209° C.                                                                        Calcd. for C.sub.12 H.sub.7 F.sub.4                                           N.sub.5 O.sub.2 S:                                                                          39.89                                                                            1.95                                                                              19.39                                            (decomp.)                                                                             Found:        38.41                                                                            2.21                                                                              19.04                 164 CH.sub.2 OCH.sub.3                                                                   H   H  H  Cl    186-191° C.                                                                    Calcd. for C.sub.14 H.sub.14 ClN.sub.5                                        O.sub.3 S:    45.72                                                                            3.84                                                                              19.03                                            (decomp.)                                                                             Found:        45.46                                                                            3.88                                                                              18.97                 165 CN     H   H  H  CH.sub.3                                                                            240-245° C.                                                                    Calcd. for C.sub.14 H.sub.12 N.sub.6                                          O.sub.2 S:    51.22                                                                            3.68                                                                              25.59                                                                            9.77                                          (decomp.)                                                                             Found:        49.43                                                                            3.58                                                                              24.55                                                                            9.47               166 COCH.sub.3                                                                           H   H  H  CH.sub.3                                                                            204-207° C.                                                                    Calcd. for C.sub.15 H.sub.15 N.sub.5                                          O.sub.3 S:    52.17                                                                            4.38                                                                              20.27                                                                            9.28                                                  Found:        51.82                                                                            4.25                                                                              20.95                                                                            9.19               167 CN     H   H  H  F     201-203° C.                                                                    Calcd. for C.sub.13 H.sub.9 FN.sub.6                                          O.sub.2 S:    46.98                                                                            2.73                                                                              25.29                                                    Found:        46.41                                                                            2.81                                                                              26.01                 168 CF.sub.3                                                                             H   H  H  F     214-216° C.                                                                    Calcd. for C.sub.13 H.sub.9 F.sub.4                                           N.sub.5 O.sub.2 S:                                                                          41.60                                                                            2.42                                                                              18.66                                                    Found:        41.33                                                                            2.61                                                                              18.74                 169 CF.sub.3                                                                             H   Cl H  H     170-171° C.                                                                    Calcd. for C.sub.13 H.sub.9 ClF.sub.3                                         N.sub.5 O.sub.2 S:                                                                          39.85                                                                            2.32                                                                              17.88                                                    Found:        39.96                                                                            2.29                                                                              17.30                 170 Cl     OCH.sub.3                                                                         H  H  Cl    229-231° C.                                                                    Calcd. for C.sub.13 H.sub.11 Cl.sub.2                                         N.sub.5 O.sub.3 S:                                                                          40.21                                                                            2.86                                                                              18.04                                            (decomp.)                                                                             Found:        40.18                                                                            2.99                                                                              17.71                 171 F      H   H  H  OCH.sub.3                                                                           212-214° C.                                                                    Calcd. for C.sub.13 H.sub.12 FN.sub.5                                         O.sub.3 S:    46.28                                                                            3.58                                                                              20.76                                                    Found:        46.26                                                                            3.56                                                                              20.49                 172 F      OCH.sub.3                                                                         H  H  F     219-221° C.                                                                    Calcd. for C.sub.13 H.sub.11 F.sub.2                                          N.sub.5 O.sub.3 S:                                                                          43.94                                                                            3.12                                                                              19.71                                                    Found:        43.79                                                                            3.29                                                                              19.48                 173 F      H   H  H  NO.sub.2                                                                            227° C.                                                                        Calcd. for C.sub.12 H.sub.9 FN.sub.6                                          O.sub.2 S:    44.99                                                                            2.83                                                                              26.24                                            (decomp.)                                                                             Found:        44.63                                                                            2.51                                                                              26.46                 174 F      CH.sub.3                                                                          H  H  F     219-221° C.                                                                    Calcd. for C.sub.13 H.sub.11 F.sub.2                                          N.sub.5 O.sub.2 S:                                                                          46.01                                                                            3.27                                                                              20.64                                                    Found:        46.27                                                                            3.47                                                                              20.27                 175 CF.sub.3                                                                             H   H  H  OCH.sub.3                                                                           209-211°  C.                                                                   Calcd. for C.sub.14 H.sub.12 F.sub.3                                          N.sub.5 O.sub.3 S:                                                                          43.41                                                                            3.12                                                                              18.08                                                    Found:        43.31                                                                            3.07                                                                              17.97                 176 CF.sub.3                                                                             H   H  H  CH.sub.2 SCH.sub.3                                                                  227-229° C.                                                                    Calcd. for C.sub.15 H.sub.14 F.sub.3                                          N.sub.5 O.sub.2 S.sub.2 :                                                                   43.16                                                                            3.38                                                                              16.78                                                    Found:        43.24                                                                            3.71                                                                              16.37                 177 CF.sub.3                                                                             H   H  H  CH.sub.3                                                                            219-220° C.                                                                    Calcd. for C.sub.14 H.sub.12 F.sub.3                                          N.sub.5 O.sub.2 S:                                                                          48.41                                                                            3.48                                                                              20.17                                                    Found:        48.14                                                                            3.71                                                                              20.34                 __________________________________________________________________________

                                      TABLE VII                                   __________________________________________________________________________     ##STR46##                                                                                          Elemental Analysis                                      Cmpd.                                                                             R.sup.1                                                                         R.sup.2                                                                         R.sup.3                                                                         R.sup.4                                                                         R.sup.5                                                                         Melting Point                                                                         Analysis      C  H  N                                   __________________________________________________________________________    178 Cl                                                                              H H H Cl                                                                              133°-134.5° C.                                                          Calcd. for C.sub.13 H.sub.11 Cl.sub.2 N.sub.5                                 O.sub.3 S:    40.22                                                                            2.83                                                                             18.03                               179 Cl                                                                              H H H H 195-196° C.                                                                    Found:        40.05                                                                            2.88                                                                             17.86                               __________________________________________________________________________

                                      TABLE VIII                                  __________________________________________________________________________     ##STR47##                                                                                                  Elemental Analysis                              Cmpd.                                                                             R.sup.1                                                                             R.sup.2                                                                          R.sup.3                                                                         R.sup.4                                                                          R.sup.5                                                                           Melting Point                                                                         Analysis      C  H  N                           __________________________________________________________________________    180 Cl    H  H H  Cl  268°-269.5° C.                                                          Calcd. for C.sub.12 H.sub.9 Cl.sub.2                                          N.sub.5 O.sub.2 S:                                                                          40.24                                                                            2.51                                                                             19.54                                             (decomp.)                                                                             Found:        40.19                                                                            2.68                                                                             19.06                       181 F     H  H H  Cl  270-273° C.                                                                    Calcd. for C.sub.12 H.sub.9 ClFN.sub.5                                        O.sub.2 S:    42.17                                                                            2.65                                                                             20.49                                                     Found:        42.09                                                                            2.63                                                                             19.91                       182 Cl    CH.sub.3                                                                         H H  Cl  257-263° C.                                                                    Calcd. for C.sub.13 H.sub.11 Cl.sub.2                                         N.sub.5 O.sub.2 S:                                                                          41.91                                                                            2.98                                                                             18.82                                                     Found:        41.88                                                                            2.86                                                                             18.30                       183 CF.sub.3                                                                            H  H H  H   171-185° C.                                                                    Calcd. for C.sub.13 H.sub.10 F.sub.3                                          N.sub.5 O.sub.2 S:                                                                          43.70                                                                            2.82                                                                             19.60                                                     Found:        42.33                                                                            2.66                                                                             19.36                       184 NO.sub.2                                                                            H  H H  CH.sub.3                                                                          200-205° C.                                                                    Calcd. for C.sub.13 H.sub.12 N.sub.6                                          O.sub.4 S:    44.82                                                                            3.47                                                                             24.13                                                     Found:        44.43                                                                            3/43                                                                             23.81                       185 F     H  H H  F   255-257° C.                                                                    Calcd. for C.sub.12 H.sub.9 F.sub.2 N.sub.5                                   O.sub.2 S:    44.30                                                                            2.79                                                                             21.53                                                     Found:        44.08                                                                            3.08                                                                             21.32                       186 Cl    H  H H  CH.sub.3                                                                          229.5-233° C.                                                                  Calcd. for C.sub.13 H.sub.12 ClN.sub.5                                        O.sub.2 S:    46.22                                                                            3.58                                                                             20.74                                                     Found:        45.56                                                                            3.93                                                                             20.27                       187 COOCH.sub.3                                                                         H  H H  F   200-201° C.                                                                    Calcd. for C.sub.14 H.sub.12 FN.sub.5                                         O.sub.4 S:    46.03                                                                            3.31                                                                             19.17                                                     Found:        45.75                                                                            3.25                                                                             19.20                       188 NO.sub.2                                                                            H  H CH.sub.3                                                                         CH.sub.3                                                                          233-236° C.                                                                    Calcd. for C.sub.1 H.sub.14 N.sub.6 O.sub.4                                   S:            46.40                                                                            3.89                                                                             23.19                                                     Found:        46.29                                                                            3.67                                                                             22.84                       189 COOCH.sub.3                                                                         H  H H  CH.sub.3                                                                          167-167.5° C.                                                                  Calcd. for C.sub.15 H.sub.15 N.sub.5                                          O.sub.4 S:    49.86                                                                            4.18                                                                             19.38                                                     Found:        49.78                                                                            4.10                                                                             19.16                       190 F     CH.sub.3                                                                         H H  F   256-258° C.                                                                    Calcd. for C.sub.13 H.sub.11 F.sub.2                                          N.sub.5 O.sub.2 S:                                                                          46.02                                                                            3.27                                                                             20.64                                                     Found:        44.95                                                                            3.00                                                                             20.00                       191 CF.sub.3                                                                            H  H H  OCH.sub.3                                                                         260-262° C.                                                                    Calcd. for C.sub.14 H.sub.12 F.sub.3                                          N.sub.5 O.sub.3 S:                                                                          43.41                                                                            3.12                                                                             18.08                                                     Found:        42.83                                                                            3.18                                                                             19.74                       __________________________________________________________________________

                                      TABLE IX                                    __________________________________________________________________________     ##STR48##                                                                                               Elemental Analysis                                 Cmpd.                                                                             R.sup.1                                                                            R.sup.2                                                                          R.sup.3                                                                         R.sup.4                                                                         R.sup.5                                                                          Melting Point                                                                         Analysis      C  H  N  S                           __________________________________________________________________________    192 Cl   H  H H Cl 249° C.                                                                        Calcd. for C.sub.12 H.sub.10 Cl.sub.2 N.sub.5                                 O.sub.2 S:    40.21                                                                            40.21                                                                            19.56                                                                            8.94                                           (decomp.)                                                                             Found:        39.99                                                                            2.66                                                                             19.62                                                                            8.70                        193 F    H  H H F  263-265° C.                                                                    Calcd. for C.sub.12 H.sub.9 F.sub.2 N.sub.5                                   O.sub.2 S:    44.30                                                                            2.79                                                                             21.53                                                                            9.86                                                   Found:        44.37                                                                            2.92                                                                             20.98                                                                            9.85                        194 Cl   CH.sub.3                                                                         H H Cl 276-280° C.                                                                    Calcd. for C.sub.13 H.sub.11 Cl.sub.2 N.sub.5                                 O.sub.2 S:    41.94                                                                            2.98                                                                             18.82                                                                            8.61                                                   Found:        41.59                                                                            2.97                                                                             19.13                                                                            8.46                        195 Cl   H  H H CH.sub.3                                                                         227-232° C.                                                                    Calcd. for C.sub.13 H.sub.12 ClN.sub.5 O.sub.2                                S:            46.22                                                                            3.58                                                                             20.74                                                                            9.49                                                   Found:        45.73                                                                            3.47                                                                             20.94                                                                            9.49                        196 NO.sub.2                                                                           H  H H CH.sub.3                                                                         251-253° C.                                                                    Calcd. for C.sub.13 H.sub.12 N.sub.6 O.sub.4                                  S:            44.82                                                                            3.47                                                                             24.13                                                                            9.20                                                   Found:        43.84                                                                            3.39                                                                             24.05                                                                            9.28                        197 COOMe                                                                              H  H H CH.sub.3                                                                         208.5-210.5° C.                                                                Calcd. for C.sub.15 H.sub.15 N.sub.5 O.sub.4                                  S:            49.85                                                                            4.18                                                                             19.38                                                     Found:        49.96                                                                            4.14                                                                             19.75                          __________________________________________________________________________

                                      TABLE X                                     __________________________________________________________________________     ##STR49##                                                                                              Elemental Analysis                                  Cmpd.                                                                             R.sup.1                                                                          R.sup.2                                                                          R.sup.3                                                                          R.sup.4                                                                          R.sup.5                                                                          Melting Point                                                                        Analysis      C  H  N                               __________________________________________________________________________    198 Cl H  H  H  H  174-176° C.                                                                   Calcd. for C.sub.13 H.sub.11 Cl.sub.2 N.sub.5                                 O.sub.2 S:    41.95                                                                            2.98                                                                             18.82                                                     Found:        41.64                                                                            2.84                                                                             18.54                           199 Cl CH.sub.3                                                                         H  H  Cl 231-233° C.                                                                   Calcd. for C.sub.14 H.sub.12 Cl.sub.3 N.sub.5                                 O.sub.2 S:    39.96                                                                            2.88                                                                             18.65                                                     Found:        39.94                                                                            2.88                                                                             18.15                           200 Cl H  H  H  Cl 171° C.                                                                       Calcd. for C.sub.13 H.sub.10 Cl.sub.3 N.sub.5                                 O.sub.2 S:    38.39                                                                            2.48                                                                             17.22                                              (decomp.)                                                                            Found:        38.47                                                                            2.66                                                                             17.37                           __________________________________________________________________________

                                      TABLE XI                                    __________________________________________________________________________     ##STR50##                                                                                              Elemental Analysis                                  Cmpd.                                                                             R.sup.1                                                                          R.sup.2                                                                          R.sup.3                                                                          R.sup.4                                                                          R.sup.5                                                                          Melting Point                                                                        Analysis      C  H  N                               __________________________________________________________________________    201 CF.sub.3                                                                         H  H  H  H  75-78° C.                                                                     Calcd. for C.sub.14 H.sub.12 F.sub.3 N.sub.5                                  O.sub.3 S:    43.36                                                                            3.09                                                                             18.06                                              (decomp.)                                                                            Found:        43.53                                                                            3.17                                                                             17.50                           202 Cl H  H  H  CH.sub.3                                                                         105-110° C.                                                                   Calcd. for C.sub.14 H.sub.14 ClN.sub.5 O.sub.3                                S:            45.66                                                                            3.80                                                                             19.02                                              (decomp.)                                                                            Found:        43.74                                                                            3.80                                                                             18.76                           203 Cl H  H  H  Cl 215-216° C.                                                                   Calcd. for C.sub.12 H.sub.12 Cl.sub.2 N.sub.5                                 O.sub.2 S:    40.21                                                                            2.83                                                                             18.04                                                     Found:        40.13                                                                            2.96                                                                             17.99                           __________________________________________________________________________

                                      TABLE XII                                   __________________________________________________________________________     ##STR51##                                                                                           Elemental Analysis                                     Cmpd.                                                                             R.sup.1                                                                         R.sup.2                                                                         R.sup.3                                                                         R.sup.4                                                                         R.sup.5                                                                         Melting Point                                                                        Analysis      C  H  N  S                                 __________________________________________________________________________    204 Cl                                                                              H H H Cl                                                                              214-216° C.                                                                   Calcd. for C.sub.14 H.sub.13 Cl.sub.2 N.sub.5                                 O.sub.2 S:    43.51                                                                            3.37                                                                             18.13                                                                            8.30                                                   Found:        43.50                                                                            3.28                                                                             17.63                                                                            7.96                              __________________________________________________________________________

                                      TABLE XIII                                  __________________________________________________________________________     ##STR52##                                                                                              Elemental Analysis                                  Cmpd.                                                                             R.sup.1                                                                          R.sup.2                                                                          R.sup.3                                                                          R.sup.4                                                                          R.sup.5                                                                          Melting Point                                                                        Analysis      C  H  N                               __________________________________________________________________________    205 Cl H  H  H  Cl 235-237° C.                                                                   Calcd. for C.sub.13 H.sub.11 Cl.sub.2 N.sub.5                                 O.sub.2 S:    41.93                                                                            2.95                                                                             18.81                                                     Found:        41.80                                                                            3.08                                                                             18.65                           __________________________________________________________________________

                                      TABLE XIV                                   __________________________________________________________________________     ##STR53##                                                                    Cmpd.                                                                             R.sup.1                                                                         R.sup.2                                                                         R.sup.3                                                                         R.sup.4                                                                         R.sup.5                                                                         Melting Point                                                                        Elemental Analysis                                       __________________________________________________________________________    206 Cl                                                                              H H H Cl                                                                              215-216° C.                                                                   Exact mass calcd. for C.sub.12 H.sub.8 BrCl.sub.2                             N.sub.5 O.sub.2 S:  438.8898                                                  Found:              438.8899                             __________________________________________________________________________

                                      TABLE XV                                    __________________________________________________________________________     ##STR54##                                                                                         Elemental Analysis                                       Cmpd.                                                                             R.sup.1                                                                         R.sup.2                                                                         R.sup.3                                                                         R.sup.4                                                                         R.sup.5                                                                         Melting Point                                                                        Analysis      C  H  N                                    __________________________________________________________________________    207 Cl                                                                              H H H Cl                                                                              105-110° C.                                                                   Calcd. for C.sub.12 H.sub.8 Cl.sub.3 N.sub.5 O.sub.2                          S:            36.69                                                                            2.04                                                                             17.80                                                     Found:        36.28                                                                            2.15                                                                             18.41                                __________________________________________________________________________

                                      TABLE XVI                                   __________________________________________________________________________     ##STR55##                                                                                         Elemental Analysis                                       Cmpd.                                                                             R.sup.1                                                                         R.sup.2                                                                         R.sup.3                                                                         R.sup.4                                                                         R.sup.5                                                                         Melting Point                                                                        Analysis      C  N  H                                    __________________________________________________________________________    208 Cl                                                                              H H H Cl                                                                              235-237° C.                                                                   Calcd. for C.sub.12 H.sub.9 Cl.sub.2 N.sub.5 O.sub.3                          S:            38.51                                                                            2.41                                                                             18.72                                                     Found:        38.29                                                                            2.44                                                                             18.92                                __________________________________________________________________________

                                      TABLE XVII                                  __________________________________________________________________________     ##STR56##                                                                                                  Elemental Analysis                              Cmpd.                                                                             R.sup.1                                                                         R.sup.2                                                                         R.sup.3                                                                         R.sup.4                                                                         R.sup.5                                                                         Melting Point                                                                        Analysis       C  H  N                                   __________________________________________________________________________    209 Cl                                                                              H H H Cl                                                                              266-269° C.                                                                   Calcd. for C.sub.13 H.sub.8 Cl.sub.2 F.sub.3 N.sub.5                          O.sub.3 S:     35.29                                                                            1.81                                                                             15.84                                                    Found:         35.14                                                                            1.72                                                                             15.65                               __________________________________________________________________________

                                      TABLE XVIII                                 __________________________________________________________________________     ##STR57##                                                                                         Elemental Analysis                                       Cmpd.                                                                             R.sup.1                                                                         R.sup.2                                                                         R.sup.3                                                                         R.sup.4                                                                         R.sup.5                                                                         Melting Point                                                                        Analysis      C  H  N                                    __________________________________________________________________________    210 Cl                                                                              H H H Cl                                                                              230-233° C.                                                                   Calcd. for C.sub.13 H.sub.11 Cl.sub.2 N.sub.5                                 O.sub.3 S:    40.21                                                                            2.83                                                                             18.03                                                     Found:        40.10                                                                            2.76                                                                             17.87                                __________________________________________________________________________

                                      TABLE XIX                                   __________________________________________________________________________     ##STR58##                                                                                         Elemental Analysis                                       Cmpd.                                                                             R.sup.1                                                                         R.sup.2                                                                         R.sup.3                                                                         R.sup.4                                                                         R.sup.5                                                                         Melting Point                                                                        Analysis      C  H  N                                    __________________________________________________________________________    211 Cl                                                                              H H H Cl                                                                              239-243° C.                                                                   Calcd. for C.sub.12 H.sub.9 Cl.sub.2 N.sub.5 O.sub.2                          S.sub.2 :     36.92                                                                            2.31                                                                             17.95                                              (decomp.)                                                                            Found:        36.51                                                                            2.41                                                                             17.68                                __________________________________________________________________________

                                      TABLE XX                                    __________________________________________________________________________     ##STR59##                                                                                         Elemental Analysis                                       Cmpd.                                                                             R.sup.1                                                                         R.sup.2                                                                         R.sup.3                                                                         R.sup.4                                                                         R.sup.5                                                                         Melting Point                                                                        Analysis      C  N  H  S                                 __________________________________________________________________________    212 Cl                                                                              H H H Cl                                                                              >310° C.                                                                      Calcd. for C.sub.13 H.sub.12 Cl.sub.2 N.sub.6                                 O.sub.2 S:    40.31                                                                            3.10                                                                             21.71                                                                            8.28                                                   Found:        40.31                                                                            3.05                                                                             22.31                                                                            7.99                              __________________________________________________________________________

                                      TABLE XXI                                   __________________________________________________________________________     ##STR60##                                                                                                  Elemental Analysis                              Cmpd.                                                                             R.sup.1                                                                             R.sup.2                                                                          R.sup.3                                                                         R.sup.4                                                                          R.sup.5                                                                           Melting Point                                                                         Analysis      C  H  N                           __________________________________________________________________________    213 Cl    H  H H  Cl  235-242° C.                                                                    Calcd. for C.sub.13 H.sub.11 Cl.sub.2                                         N.sub.5 O.sub.3 S:                                                                          40.21                                                                            2.84                                                                             18.04                                             (decomp.)                                                                             Found:        40.37                                                                            2.78                                                                             18.06                       214 F     H  H H  F   230-232° C.                                                                    Calcd. for C.sub.13 H.sub.11 F.sub.2                                          N.sub.5 O.sub.3 S:                                                                          43.94                                                                            3.12                                                                             19.71                                                     Found:        43.80                                                                            3.10                                                                             20.11                       215 COOCH.sub.3                                                                         H  H H  F   195-197° C.                                                                    Calcd. for C.sub.15 H.sub.14 FN.sub.5                                         O.sub.5 S:    45.57                                                                            3.57                                                                             17.71                                                     Found:        45.26                                                                            3.51                                                                             18.12                       216 COOCH.sub.3                                                                         H  H H  CH.sub.3                                                                          197-198° C.                                                                    Calcd. for C.sub.16 H.sub.17 N.sub.5                                          O.sub.5 S:    49.10                                                                            4.38                                                                             17.89                                                     Found:        48.95                                                                            4.28                                                                             17.88                       217 CF.sub.3                                                                            H  H H  H   213-215° C.                                                                    Calcd. for C.sub.14 H.sub.12 F.sub.3                                          N.sub.5 O.sub.3 S:                                                                          43.41                                                                            3.12                                                                             18.08                                                     Found:        42.90                                                                            3.21                                                                             18.48                       218 Cl    CH.sub.3                                                                         H H  Cl  240.5-241.5° C.                                                                Calcd. for C.sub.14 H.sub.13 Cl.sub.2                                         N.sub.5 O.sub.3 S:                                                                          41.80                                                                            3.26                                                                             17.41                                                     Found:        41.64                                                                            3.28                                                                             17.56                       219 F     CH.sub.3                                                                         H H  F   230-231° C.                                                                    Calcd. for C.sub.14 H.sub.13 F.sub.2                                          N.sub.5 O.sub.3 S:                                                                          45.53                                                                            3.55                                                                             18.96                                                     Found:        45.16                                                                            3.55                                                                             19.37                       220 Cl    H  H H  CH.sub.3                                                                          213-214° C.                                                                    Calcd. for C.sub.14 H.sub.14 ClN.sub.5                                        O.sub.3 S:    45.72                                                                            3.84                                                                             19.04                                                     Found:        45.96                                                                            3.90                                                                             19.40                       221 NO.sub.2                                                                            H  H H  CH.sub.3                                                                          226-228° C.                                                                    Calcd. for C.sub.14 H.sub.14 N.sub.6                                          O.sub.5 S:    44.44                                                                            3.73                                                                             22.21                                                     Found:        44.52                                                                            3.75                                                                             22.50                       222 NO.sub.2                                                                            H  H CH.sub.3                                                                         CH.sub.3                                                                          230-231° C.                                                                    Calcd. for C.sub.15 H.sub.16 N.sub.6                                          O.sub.5 S:    45.91                                                                            4.11                                                                             21.42                                                     Found:        45.49                                                                            4.04                                                                             21.64                       223 CF.sub.3                                                                            H  H H  OCH.sub.3                                                                         232-233° C.                                                                    Calcd. for C.sub.15 H.sub.14 F.sub.3                                          N.sub.5 O.sub.4 S:                                                                          43.17                                                                            3.38                                                                             16.78                                                     Found:        43.10                                                                            3.42                                                                             16.92                       __________________________________________________________________________

                                      TABLE XXII                                  __________________________________________________________________________     ##STR61##                                                                                         Elemental Analysis                                       Cmpd.                                                                             R.sup.1                                                                         R.sup.2                                                                         R.sup.3                                                                         R.sup.4                                                                         R.sup.5                                                                         Melting Point                                                                        Analysis      C  H  N                                    __________________________________________________________________________    224 Cl                                                                              H H H Cl                                                                              220° C.                                                                       Calcd. for C.sub.13 H.sub.9 Cl.sub.2 N.sub.5 O.sub.4                          S:            38.80                                                                            2.24                                                                             17.41                                              (decomp.)                                                                            Found:        39.30                                                                            2.66                                                                             17.41                                __________________________________________________________________________

                                      TABLE XXIII                                 __________________________________________________________________________     ##STR62##                                                                                         Elemental Analyis                                        Cmpd.                                                                             R.sup.1                                                                         R.sup.2                                                                         R.sup.3                                                                         R.sup.4                                                                         R.sup.5                                                                         Melting Point                                                                        Analysis      C  H  N                                    __________________________________________________________________________    225 Cl                                                                              H H H Cl                                                                              310-320° C.                                                                   Calcd. for C.sub.11 H.sub.7 Cl.sub.2 N.sub.5 O.sub.3                          S:            36.65                                                                            1.94                                                                             19.40                                              (decomp.)                                                                            Found:        36.79                                                                            1.76                                                                             19.14                                __________________________________________________________________________

                                      TABLE XXIV                                  __________________________________________________________________________     ##STR63##                                                                                         Elemental Analysis                                       Cmpd.                                                                             R.sup.1                                                                         R.sup.2                                                                         R.sup.3                                                                         R.sup.4                                                                         R.sup.5                                                                         Melting Point                                                                        Analysis      C  H  N                                    __________________________________________________________________________    226 Cl                                                                              H H H Cl                                                                              285-287° C.                                                                   Calcd. for C.sub.17 H.sub.10 Cl.sub.2 N.sub.6                                 O.sub.4 S:    43.84                                                                            2.15                                                                             18.00                                                     Found:        44.12                                                                            2.43                                                                             17.45                                __________________________________________________________________________

                                      TABLE XXV                                   __________________________________________________________________________     ##STR64##                                                                                               Elemental Analysis                                 Cmpd.                                                                             R.sup.1                                                                          R.sup.2                                                                          R.sup.3                                                                         R.sup.4                                                                         R.sup.5                                                                             Melting Point                                                                        Analysis       C  H  N                             __________________________________________________________________________    227 Cl H  H H Cl    237-239° C.                                                                   Calcd. for C.sub.13 H.sub.8 Cl.sub.2 F.sub.3                                  N.sub.5 O.sub.2 S:                                                                           36.63                                                                            1.88                                                                             16.42                                                    Found:         36.74                                                                            1.52                                                                             16.94                         228 F  H  H H F     234-237° C.                                                                   Calcd. for C.sub.13 H.sub.8 F.sub.5 N.sub.5                                   O.sub.2 S:     39.74                                                                            2.04                                                                             17.83                                                    Found:         39.49                                                                            2.08                                                                             18.11                         229 Cl CH.sub.3                                                                         H H Cl    252-254° C.                                                                   Calcd. for C.sub.14 H.sub.10 Cl.sub.2 F.sub.3                                 N.sub.5 O.sub.2 S:                                                                           38.21                                                                            2.27                                                                             15.97                                                    Found:         38.09                                                                            2.34                                                                             16.40                         230 F  CH.sub.3                                                                         H H F     243-245° C.                                                                   Calcd. for C.sub.14 H.sub.10 F.sub.5 N.sub.5                                  O.sub.2 S:     41.32                                                                            2.46                                                                             17.23                                                    Found:         41.21                                                                            2.51                                                                             17.49                         231 CF.sub.3                                                                         H  H H OCH.sub.3                                                                           226-229° C.                                                                   Calcd. for C.sub.15 H.sub.11 F.sub.6 N.sub.5                                  O.sub.3 S:     39.61                                                                            2.42                                                                             15.40                                                    Found:         39.50                                                                            2.52                                                                             15.60                         307 Cl H  H H CH.sub.3                                                                            234-235° C.                                                                   Calcd. for C.sub.14 H.sub.11 ClF.sub.3 N.sub.5                                OS:            41.14                                                                            2.73                                                                             17.26                                                    Found:         41.03                                                                            2.77                                                                             17.14                         308 Cl H  H H CH.sub.2 OCH.sub.3                                                                  206-207° C.                                                                   Calc. for C.sub.15 H.sub.13 ClF.sub.3 N.sub.5                                 O.sub.3 S      41.34                                                                            3.01                                                                             16.07                                                    Found:         41.19                                                                            2.97                                                                             16.02                         __________________________________________________________________________

                                      TABLE XXVI                                  __________________________________________________________________________     ##STR65##                                                                                         Elemental Analysis                                       Cmpd.                                                                             R.sup.1                                                                         R.sup.2                                                                         R.sup.3                                                                         R.sup.4                                                                         R.sup.5                                                                         Melting Point                                                                        Analysis      C  H  N                                    __________________________________________________________________________    232 Cl                                                                              H H H Cl                                                                              >310° C.                                                                      Calcd. for C.sub.12 H.sub.9 Cl.sub.2 N.sub.5 O.sub.3                          S:            38.51                                                                            2.41                                                                             18.72                                                     Found:        38.28                                                                            2.44                                                                             19.03                                __________________________________________________________________________

                                      TABLE XXVII                                 __________________________________________________________________________     ##STR66##                                                                                         Elemental Analysis                                       Cmpd.                                                                             R.sup.1                                                                         R.sup.2                                                                         R.sup.3                                                                         R.sup.4                                                                         R.sup.5                                                                         Melting Point                                                                        Analysis      C  H  N                                    __________________________________________________________________________    233 Cl                                                                              H H H CH.sub.3                                                                        221-224° C.                                                                   Calcd. for C.sub.15 H.sub.14 ClN.sub.5 O.sub.2                                              29.52                                                                            3.85                                                                             19.27                                              (decomp.)                                                                            Found:        49.56                                                                            3.85                                                                             18.90                                __________________________________________________________________________

                                      TABLE XXVIII                                __________________________________________________________________________     ##STR67##                                                                    Cmpd.                                                                             R.sup.1                                                                         R.sup.2                                                                         R.sup.3                                                                         R.sup.4                                                                         R.sup.5                                                                         Melting Point                                                                        Elemental Analysis                                       __________________________________________________________________________    234 Cl                                                                              H H H Cl                                                                              80-92° C.                                                                     Exact mass calcd. for C.sub.13 H.sub.11 Cl.sub.2                              N.sub.5 O.sub.2 S: 327.9981                                            (decomp.)                                                                            Found:             327.9994                              __________________________________________________________________________

                                      TABLE XXIX                                  __________________________________________________________________________     ##STR68##                                                                                         Elemental Analysis                                       Cmpd.                                                                             R.sup.1                                                                         R.sup.2                                                                         R.sup.3                                                                         R.sup.4                                                                         R.sup.5                                                                         Melting Point                                                                        Analysis      C  H  N                                    __________________________________________________________________________    235 Cl                                                                              H H H Cl                                                                              254-258° C.                                                                   Calcd. for C.sub.13 H.sub.11 Cl.sub.2 N.sub.5                                 O.sub.2 S.sub.2 :                                                                           36.96                                                                            2.60                                                                             16.58                                              (decomp.)                                                                            Found:        36.92                                                                            2.44                                                                             16.57                                __________________________________________________________________________

                                      TABLE XXX                                   __________________________________________________________________________     ##STR69##                                                                                         Elemental Analysis                                       Cmpd.                                                                             R.sup.1                                                                         R.sup.2                                                                         R.sup.3                                                                         R.sup.4                                                                         R.sup.5                                                                         Melting Point                                                                        Analysis       C  H  N                                   __________________________________________________________________________    236 Cl                                                                              H H H Cl                                                                              250-253° C.                                                                   Calcd. for C.sub.14 H.sub.10 Cl.sub.2 F.sub.3                                 N.sub.5 O.sub.3 S:                                                                           36.85                                                                            2.19                                                                             15.35                                             (decomp.)                                                                            Found:         36.44                                                                            2.07                                                                             15.62                               __________________________________________________________________________

                                      TABLE XXXI                                  __________________________________________________________________________     ##STR70##                                                                                         Elemental Analysis                                       Cmpd.                                                                             R.sup.1                                                                         R.sup.2                                                                         R.sup.3                                                                         R.sup.4                                                                         R.sup.5                                                                         Melting Point                                                                        Analysis       C  H  N                                   __________________________________________________________________________    237 Cl                                                                              H H H Cl                                                                              270-274° C.                                                                   Calcd. for C.sub.14 H.sub.14 Cl.sub.2 N.sub.6                                 O.sub.2 S:     41.89                                                                            3.49                                                                             20.95                                             (decomp.)                                                                            Found:         41.87                                                                            3.49                                                                             21.03                               __________________________________________________________________________

                                      TABLE XXXII                                 __________________________________________________________________________     ##STR71##                                                                                         Elemental Analysis                                       Cmpd.                                                                             R.sup.1                                                                         R.sup.2                                                                         R.sup.3                                                                         R.sup.4                                                                         R.sup.5                                                                         Melting Point                                                                        Analysis       C  H  N                                   __________________________________________________________________________    238 Cl                                                                              H H H Cl                                                                              286-287° C.                                                                   Calcd. for C.sub.13 H.sub.5 Cl.sub.2 F.sub.6 N.sub.5                          O.sub.2 S:     32.56                                                                            1.04                                                                             14.59                                                    Found:         32.98                                                                            0.70                                                                             14.71                               __________________________________________________________________________

                                      TABLE XXXIII                                __________________________________________________________________________     ##STR72##                                                                                         Elemental Analysis                                       Cmpd.                                                                             R.sup.1                                                                         R.sup.2                                                                         R.sup.3                                                                         R.sup.4                                                                         R.sup.5                                                                         Melting Point                                                                        Analysis       C  H  N                                   __________________________________________________________________________    239 Cl                                                                              H H H Cl                                                                              284-286° C.                                                                   Calcd. for C.sub.20 H.sub.21 Cl.sub.2 N.sub.5                                 O.sub.3 S:     49.90                                                                            4.36                                                                             14.52                                                    Found:         49.81                                                                            4.22                                                                             14.28                               __________________________________________________________________________

                                      TABLE XXXIV                                 __________________________________________________________________________     ##STR73##                                                                                         Elemental Analysis                                       Cmpd.                                                                             R.sup.1                                                                         R.sup.2                                                                         R.sup.3                                                                         R.sup.4                                                                         R.sup.5                                                                         Melting Point                                                                        Analysis      C  H  N                                    __________________________________________________________________________    240 Cl                                                                              H H H Cl                                                                              236-239° C.                                                                   Calcd. for C.sub.15 H.sub.13 Cl.sub.2 N.sub.5                                 O.sub.4 S:    41.86                                                                            3.02                                                                             16.28                                              (decomp.)                                                                            Found:        41.75                                                                            2.79                                                                             16.16                                __________________________________________________________________________

                                      TABLE XXXV                                  __________________________________________________________________________     ##STR74##                                                                                         Elemental Analysis                                       Cmpd.                                                                             R.sup.1                                                                         R.sup.2                                                                         R.sup.3                                                                         R.sup.4                                                                         R.sup.5                                                                         Melting Point                                                                        Analysis        C  H  N                                  __________________________________________________________________________    241 Cl                                                                              H H H Cl                                                                              120-130° C.                                                                   Calcd. for C.sub.13 H.sub.9 Cl.sub.2 N.sub.5 O.sub.4                          S.H.sub.2 O:    37.15                                                                            2.38                                                                             16.70                                            (decomp.)                                                                            Found:          37.03                                                                            2.02                                                                             17.16                              __________________________________________________________________________

                                      TABLE XXXVI                                 __________________________________________________________________________     ##STR75##                                                                                           Elemental Analysis                                     Cmpd.                                                                             R.sup.1                                                                          R.sup.2                                                                          R.sup.3                                                                         R.sup.4                                                                         R.sup.5                                                                         Melting Point                                                                        Analysis      C  H  N                                  __________________________________________________________________________    242 Cl H  H H Cl                                                                              280-304° C.                                                                   Calcd. for C.sub.12 H.sub.9 Cl.sub.2 N.sub.5                                  O.sub.3 S:    38.51                                                                            2.41                                                                             18.72                                              (decomp.)                                                                            Found:        38.52                                                                            2.49                                                                             19.03                              309 F  CH.sub.3                                                                         H H F 304-305° C.                                                                   Calcd. for C.sub.13 H.sub.11 F.sub.2 N.sub.5                                  O.sub.3 S:    43.94                                                                            3.12                                                                             19.71                                                     Found:        43.86                                                                            2.91                                                                             19.79                              310 CF.sub.3                                                                         H  H H H 245-247° C.                                                                   Calcd. for C.sub.13 H.sub.10 F.sub.3 N.sub.5                                  O.sub.3 S:    40.37                                                                            3.00                                                                             8.29                                                                    40.41                                                                            2.76                                                                             7.93                               __________________________________________________________________________

                                      TABLE XXXVII                                __________________________________________________________________________     ##STR76##                                                                                         Elemental Analysis                                       Cmpd.                                                                             R.sup.1                                                                         X  Y Z  Melting Point                                                                        Analysis      C  H  N                                    __________________________________________________________________________    243 Cl                                                                              CH.sub.3                                                                         H CH.sub.3                                                                         303-306° C.                                                                   Calcd. for C.sub.17 H.sub.14 ClN.sub.5 O.sub.2                                              52.65                                                                            3.64                                                                             18.05                                              (decomp.)                                                                            Found:        52.10                                                                            3.65                                                                             18.51                                244 Cl                                                                              H  H CH.sub.3                                                                         262-265° C.                                                                   Calcd. for C.sub.16 H.sub.12 ClN.sub.5 O.sub.2                                              51.41                                                                            3.24                                                                             18.73                                              (decomp.)                                                                            Found:        50.97                                                                            3.29                                                                             18.99                                __________________________________________________________________________

                                      TABLE XXXVIII                               __________________________________________________________________________     ##STR77##                                                                                            Elemental Analysis                                    Cmpd.                                                                             R.sup.1                                                                            X  Y Z  Melting Point                                                                        Analysis       C  H  N                                __________________________________________________________________________    245 COOMe                                                                              CH.sub.3                                                                         H CH.sub.3                                                                         206-208° C.                                                                   Calcd. for C.sub.19 H.sub.17 N.sub.5 O.sub.4                                  S.1/2H.sub.2 O:                                                                              54.28                                                                            4.32                                                                             16.65                                                    Found:         53.98                                                                            4.12                                                                             16.83                            __________________________________________________________________________

                                      TABLE XXXIX                                 __________________________________________________________________________     ##STR78##                                                                                                         Elemental Analysis                       Cmpd.                                                                             Pyrazole                                                                           R.sup.2                                                                            R.sup.3                                                                            X    Y  Z  Melting Point                                                                        Analysis      C   H   N                  __________________________________________________________________________    246 A    CF.sub.3                                                                           CH.sub.3                                                                           H       CH.sub.3                                                                         273-274° C.                                                                   Calcd. for C.sub.12 H.sub.12 F.sub.3                                          N.sub.7 O.sub.2 S:                                                                          38.39                                                                             3.22                                                                              26.12                                            (decomp.)                                                                            Found:        38.73                                                                             3.23                                                                              25.92              247 A    CF.sub.3                                                                           CH.sub.3                                                                           CH.sub.3                                                                              CH.sub.3                                                                         288-288.5° C.                                                                 Calcd. for C.sub.13 H.sub.14 F.sub.3                                          N.sub.7 O.sub.2 S:                                                                          40.09                                                                             3.62                                                                              25.18                                            (decomp.)                                                                            Found:        40.22                                                                             3.49                                                                              25.17              248 A    COOMe                                                                              CH.sub.3                                                                           H       CH.sub.3                                                                         174-175° C.                                                                   Calcd. for C.sub.13 H.sub.15 N.sub.7                                          O.sub.4 S:    42.73                                                                             4.14                                                                              26.84                                                   Found:        42.39                                                                             4.21                                                                              26.91              249 A    H    COOMe                                                                              CH.sub.3                                                                           CH.sub.3                                                                         CH.sub.3                                                                         208-210° C.                                                                   Calcd. for C.sub.14 H.sub.17 N.sub.7                                          O.sub.4 S:    44.32                                                                             4.52                                                                              25.85                                                   Found:        44.07                                                                             4.31                                                                              25.72              250 A    H    CH.sub.3                                                                           COOMe                                                                              CH.sub.3                                                                         CH.sub.3                                                                         228-230° C.                                                                   Calcd. for C.sub.14 H.sub.17 N.sub.7                                          O.sub.4 S:    44.32                                                                             4.52                                                                              25.85                                                   Found:        44.06                                                                             4.82                                                                              25.97              311 B    H    COOEt                                                                              CH.sub.3                                                                           H  CH.sub.3                                                                         217-219° C.                                                                   Calcd. for C.sub.14 H.sub.17 N.sub.7                                          O.sub.4 S:    44.31                                                                             4.52                                                                              25.85                                                   Found:        44.29                                                                             4.73                                                                              25.63              312 B    CH.sub.3                                                                           Br   CH.sub.3                                                                           H  CH.sub.3                                                                         188° C.                                                                       Calcd. for C.sub.12 H.sub.14                                                  BrN.sub.7 O.sub.2 S:                                                                        36.01                                                                             3.53                                                                              24.50                                            (decomp.)                                                                            Found:        36.07                                                                             3.74                                                                              24.27              __________________________________________________________________________

                                      TABLE XL                                    __________________________________________________________________________     ##STR79##                                                                    Cmpd.                                                                             R.sup.1                                                                         R.sup.2                                                                         R.sup.3                                                                         R.sup.4                                                                         Melting Point                                                                        Elemental Analysis                                         __________________________________________________________________________    251 Cl                                                                              H Cl                                                                              H 159°-161° C.                                                           Exact mass calcd. for C.sub.12 H.sub.10 Cl.sub.2                              N.sub.6 O.sub.2 S: 371.9963                                                   Found:             371.9973                                252 Cl                                                                              H H H >210° C.                                                                      Analysis      C  H   N                                                 (decomp.)                                                                            Calcd. for C.sub.12 H.sub.11 ClN.sub.6 O.sub.2                                              42.55                                                                            3.27                                                                              24.80                                                    Found:        42.19                                                                            3.28                                                                              24.27                                 __________________________________________________________________________

                                      TABLE XLI                                   __________________________________________________________________________     ##STR80##                                                                                       Elemental Analysis                                         Cmpd.                                                                             R.sup.1                                                                         R.sup.2                                                                         R.sup.3                                                                         R.sup.4                                                                         Melting Point                                                                        Analysis       C  H  N                                     __________________________________________________________________________    253 H H H H >250° C.                                                                      Calcd. for C.sub.12 H.sub.12 N.sub.6 O.sub.2 S.H.sub.2                        O:             44.72                                                                            4.38                                                                             26.06                                             (decomp.)                                                                            Found:         44.88                                                                            4.19                                                                             26.37                                 254 H Cl                                                                              H H >260° C.                                                                      Calcd. for C.sub.12 H.sub.11 ClN.sub.6 O.sub.2                                               42.55                                                                            3.27                                                                             24.80                                             (decomp.)                                                                            Found:         42.48                                                                            3.40                                                                             24.49                                 __________________________________________________________________________

                                      TABLE XLII                                  __________________________________________________________________________     ##STR81##                                                                    Cmpd.                                                                             R.sup.1                                                                         R.sup.2                                                                         R.sup.3                                                                         R.sup.4                                                                         Melting Point                                                                          Elemental Analysis                                       __________________________________________________________________________    255 Cl                                                                              H H H 207.5°-208.5° C.                                                         Exact mass calcd. for C.sub.12 H.sub.11 ClN.sub.6                             O.sub.2 S:         338.0352                                                   Found:             338.0342                              __________________________________________________________________________

                                      TABLE XLIII                                 __________________________________________________________________________     ##STR82##                                                                                          Elemental Analysis                                      Cmpd.                                                                              Ar        Melting Point                                                                        Analysis       C  H  N                                  __________________________________________________________________________    256                                                                                 ##STR83##                                                                              120-125° C.                                                                   Calcd. for C.sub.10 H.sub.10 N.sub.6 O.sub.2                                  S.sub.2 : Found:                                                                             38.66 38.48                                                                      3.22 3.28                                                                        27.06 26.92                        257                                                                                 ##STR84##                                                                              160-168° C.                                                                   Calcd. for C.sub.13 H.sub.13 N.sub.5 O.sub.4                                  S.sub.2 : Found:                                                                             42.49 42.04                                                                      3.53 3.40                                                                        19.05 18.81                        258                                                                                 ##STR85##                                                                              224-226° C. (decomp.)                                                         Calcd. for C.sub.14 H.sub.11 ClN.sub.6 O.sub.2                                S.sub.2 : Found:                                                                             42.58 43.10                                                                      2.78 2.79                                                                        21.27 20.74                        259                                                                                 ##STR86##                                                                              195° C. (decomp.)                                                             Calcd. for C.sub.13 H.sub.11 N.sub.8 O.sub.2 S:                               Found:         47.41 47.01                                                                      3.37 3.31                                                                        29.78 30.78                        __________________________________________________________________________

    TABLE XLIV      ##STR87##       Elemental Analysis Cmpd. R.sup.1 R.sup.2 V X Z Melting Point Analysis     C H N Cl S       260 Cl Cl CH.sub.3 CH.sub.3 CH.sub.3 220-222° C. Calcd. for     C.sub.14 H.sub.13 Cl.sub.2 N.sub.5 O.sub.2 S: 43.54 3.39 18.13     Found: 43.55 3.32 18.03 261 COOMe CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3     175.5-177° C. Calcd. for C.sub.17 H.sub.19 N.sub.5 O.sub.4 S:     52.43 4.92 17.98        Found: 52.31 4.93 17.94 262 Cl Cl COCH.sub.3     CH.sub.3 CH.sub.3 214-217° C. Calcd. for C.sub.15 H.sub.13     Cl.sub.2 N.sub.5 O.sub.3 S: 43.49 3.16 16.90        Found: 43.44 3.16     16.77 263 Cl Cl CH.sub.2 CHCH.sub.2 CH.sub.3 CH.sub.3 182-184° C.     Calcd. for C.sub.16 H.sub.15 Cl.sub.2 N.sub.5 O.sub.2 S: 46.61 3.67     16.98        Found: 46.74 3.67 16.86 264 Cl Cl CH.sub.2 COOEt CH.sub.3     CH.sub.3 173-176° C. Calcd. for C.sub.17 H.sub.17 Cl.sub.2     N.sub.5 O.sub.4 S: 44.55 3.74 15.27        Found: 44.74 3.74 15.08 265     Cl Cl CH.sub.2 Ph CH.sub.3 CH.sub.3 >240° C. Calcd. for C.sub.20     H.sub.17 Cl.sub.2 N.sub.5 O.sub.2 S.1/2H.sub.2 O: 50.97 3.85 14.85     (decomp.) Found: 50.93 3.66 14.85 266 COOMe CH.sub.3 CH.sub.2 COOEt     CH.sub.3 CH.sub.3 152-155° C. Calcd. for C.sub.20 H.sub.23     N.sub.5 O.sub.6 S: 52.05 5.02 15.17        Found: 51.64 4.94 15.39 267     COOMe CH.sub.3 CH.sub.2 Ph CH.sub.3 CH.sub.3 174-176° C. Calcd.     for C.sub.23 H.sub.23 N.sub.5 O.sub.4 S: 59.34 4.98 15.04        Found:     59.00 4.89 15.18 268 Cl Cl COCH.sub.3 H CH.sub.3 176-181° C.     Calcd. for C.sub.14 H.sub.11 Cl.sub.2 N.sub.5 O.sub.3 S: 42.02 2.77     17.49        Found: 42.28 2.90 17.16 269 Cl Cl Co.sub.-iPr H CH.sub.3     193-194.5° C. Calcd. for C.sub.16 H.sub.15 Cl.sub.2 N.sub.5     O.sub.3 S: 44.87 3.53 16.35        Found: 45.26 3.53 16.39 270 Cl Cl     COC.sub.11 H.sub.23  CH.sub.3 105.5-106.5° C. Calcd. for C.sub.24     H.sub.31 Cl.sub.2 N.sub.5 O.sub.3 S: 53.33 5.78 12.96        Found:     53.40 5.77 12.84      271 Cl Cl     ##STR88##      H CH.sub.3 234-235° C. Calcd. for C.sub.19 H.sub.11 Cl.sub.4     N.sub.5 O.sub.3 S:Found: 42.9643.31 2.092.29 13.1813.04  272 Cl Cl     CO.sub.2 Et H CH.sub.3 189-191° C. Calcd. for C.sub.15 H.sub.15     Cl.sub.2 N.sub.5 O.sub.4 S: 41.87 3.05 16.28        Found: 42.51 3.25     16.02 273 Cl Cl CON(CH.sub.3).sub.2 H CH.sub.3 225-228° C. Calcd.     for C.sub.15 H.sub.14 Cl.sub.2 N.sub.6 O.sub.3 S: 41.97 3.29 19.58     (decomp.) Found: 42.08 3.27 20.18 274 Cl Cl COPh H CH.sub.3 187-189.degre     e. C. Calcd. for C.sub.19 H.sub.13 Cl.sub.2 N.sub.5 O.sub.3 S: 49.36     2.83 15.15        Found: 48.97 2.84 15.16 275 F F COCH.sub.3 H CH.sub.3     195-200° C. Calcd. for C.sub.14 H.sub.11 F.sub.2 N.sub.5 O.sub.3     S: 45.77 3.02 19.07  8.73        Found: 45.59 3.12 19.16  8.91 276 F F     COEt H CH.sub.3 154-160° C. Calcd. for C.sub. 15 H.sub.13 F.sub.2     N.sub.5 O.sub.3 S: 47.24 3.44 18.37  8.41        Found: 47.05 3.44 18.49      8.27 277 F F COiPr H CH.sub.3 182-184° C. Calcd. for C.sub.16     H.sub.15 F.sub.2 N.sub.5 O.sub.3 S: 48.60 3.82 17.71        Found: 48.41     3.93 17.43 278 F F COCH.sub.2 tBu H CH.sub.3 158-162° C. Calcd.     for C.sub.18 H.sub.19 F.sub.2 N.sub.5 O.sub.3 S: 51.05 4.52 16.54  7.57           Found: 51.15 4.62 16.38  7.83 279 F F COnBu H CH.sub.3 131-134.degr     ee. C. Calcd. for C.sub.17 H.sub.17 F.sub.2 N.sub.5 O.sub.3 S: 49.87     4.19 17.11        Found: 49.10 4.04 17.05 280 F F COtBu H CH.sub.3     185-186° C. Calcd. for C.sub.17 H.sub.17 F.sub.2 N.sub.5 O.sub.3     S: 49.87 4.19 17.11  7.83       (decomp.) Found: 49.93 3.89 16.82  7.10     281 F F COCH.sub.2 Ph H CH.sub.3 178- 185° C. Calcd. for C.sub.20     H.sub.15 F.sub.2 N.sub.5 O.sub.3 S: 54.17 3.41 15.80        Found: 53.60     3.18 15.56 282 F F COCH.sub.2 CH.sub.2 Cl H CH.sub.3 195° C.     Calcd. for C.sub.15 H.sub.12 ClF.sub.2 N.sub.5 O.sub.3 S: 43.33 2.91     16.84 8.53 7.71       (decomp.) Found: 43.21 2.95 17.31 8.45 7.47 283 F     F COnPr H CH.sub.3 130-135° C. Calcd. for C.sub.16 H.sub.15     F.sub.2 N.sub.5 O.sub.3 S: 48.60 3.82 17.71  8.11        Found 48.42     3.81 17.91  7.98 284 F F COCH.sub.2 iPr H CH.sub.3 154-159° C.     Calcd. for C.sub.17 H.sub.17 F.sub.2 N.sub.5 O.sub.3 S: 49.87 4.19 17.11      7.83        Found 49.45 4.04 17.15  7.68 285 F F COCH.sub.2 Cl H     CH.sub.3 156-158° C. Calcd. for C.sub.14 H.sub.10 ClF.sub.2     N.sub.5 O.sub.3 S: 41.85 2.51 17.43        Found: 42.19 2.68 17.43 286 F     F COCHCH.sub.3CH.sub.2 H CH.sub.3 171.5-174° C. Calcd. for     C.sub.16 H.sub.13 F.sub.2 N.sub.5 O.sub.3 S: 48.85 3.33 17.81  8.15       Found 48.36 3.51 17.91  7.94 287 F F COnC.sub.9 H.sub.19 H CH.sub.3     97-99° C. Calcd. for C.sub.22 H.sub.27 F.sub.2 N.sub.5 O.sub.3 S:     55.10 5.68 14.61  6.69        Found 55.22 5.60 14.85  6.63 288 F F     COCHCHCH.sub.3 H CH.sub.3 154-156° C. Calcd. for C.sub.16     H.sub.13 F.sub.2 N.sub.5 O.sub.3 S: 48.85 3.33 17.81 8.15        Found:     48.41 3.41 17.94 8.49 289 F F COcycloC.sub.3      H.sub.5 H CH.sub.3 200.5-203° C. Calcd. for C.sub.16 H.sub.13     F.sub.2 N.sub.5 O.sub.3 S: 48.85 3.33 17.81  8.15        Found: 48.32     3.34 18.03  8.34 290 F F COPh H CH.sub.3 186-189° C. Calcd. for     C.sub.19 H.sub.13 F.sub.2 N.sub.5 O.sub. 3 S: 53.14 3.05 16.31  7.47        Found: 53.74 3.16 16.63  7.11 291 F F COcycloC.sub.6 H.sub.11 H     CH.sub.3 178-180° C. Calcd. for C.sub.19 H.sub.19 F.sub.2 N.sub.5     O.sub.3 S: 52.40 4.40 16.08  7.36        Found: 51.40 4.28 16.08  7.78     292 F F COCH.sub.2 OPh H CH.sub.3 141-144° C. Calcd. for C.sub.20     H.sub.15 F.sub.2 N.sub.5 O.sub.4 S: 52.28 3.29 15.25  6.98        Found:     51.77 3.38 15.28  6.76 293 F F COCHCHPh H CH.sub.3 oil Calcd. for     C.sub.21 H.sub.15 F.sub.2 N.sub.5 O.sub.3 S: 55.38 3.32 15.38  7.04       Found: 55.55 3.45 15.29  6.98 294 F F COCH.sub.2 CH.sub.2CO.sub.2     CH.sub.2 CH.sub.3 H CH.sub.3 157-162° C. Calcd. for C.sub.18     H.sub.17 F.sub.2 N.sub.5 O.sub.5 S: 47.68 3.78 15.45  7.07        Found:     47.32 3.78 15.68  7.03 295 F F CO(2-furyl) H CH.sub.3 120° C.     Calcd. for C.sub.17 H.sub.11 F.sub.2 N.sub.5 O.sub.4 S: 48.69 2.64 16.70      7.65       (decomp.) Found: 48.49 2.75 17.03  7.83 296 F F COcycloC.sub.     4 H.sub.7 H CH.sub.3 161-170° C. Calcd. for C.sub.17 H.sub.15     F.sub.2 N.sub.5 O.sub.3 S: 50.12 3.71 17.19  7.87        Found: 49.58     3.89 17.21  8.07 297 F F SO.sub.2 CH.sub.3 H CH.sub.3 193-195° C.     Calcd. for C.sub.13 H.sub.11 F.sub.2 N.sub.5 O.sub.4 S.sub.2 : 38.71     2.75 17.36  15.90        Found: 38.98 2.92 17.18  15.72 298 F F SO.sub.2     Ph H CH.sub.3 182-190° C. Calcd. for C.sub.18 H.sub.13 F.sub.2     N.sub.5 O.sub.4 S.sub.2 : 46.45 2.82 15.05  13.78        Found: 46.41     3.03 14.79  14.01 299 F F CH.sub.2 Ph H CH.sub.3 170-177° C.     Calcd. for C.sub.9 H.sub.15 F.sub.2 N.sub. 5 O.sub.2 S: 54.93 3.64 16.86      7.72        Found 54.45 3.73 16.63  7.77 300 F F CO(SEt) H CH.sub.3     197-199° C. Calcd. for C.sub.15 H.sub.13 F.sub.2 N.sub.5 O.sub.3     S.sub.2 : 43.58 3.17 16.94  15.51        Found: 43.45 3.19 17.12  15.64     301 F F CH.sub.2 (4-NO.sub.2 Ph) H CH.sub.3 194-200° C. Calcd.     for C.sub.19 H.sub.14 F.sub.2 N.sub.6 O.sub.4 S: 49.64 3.07 18.26  6.96           Found 49.64 3.25 18.40  6.88 302 F F CH.sub.2 (4-MeOPh) H CH.sub.3     156-158° C. Calcd. for C.sub.20 H.sub.17 F.sub.2 N.sub.5 O.sub.3     S: 53.92 3.85 15.72  7.20        Found 53.65 3.98 15.95  7.46 303 F F     CH.sub.2 (2-furyl) H CH.sub.3 177-180° C. Calcd. for C.sub.17     H.sub.13 F.sub.2 N.sub.5 O.sub.3 S: 50.37 3.23 17.28  7.91        Found:     50.50 3.30 17.33  7.74 313 F F CH.sub.2      SCH.sub.3 H CH.sub.3 195-200° C. Calcd. for C.sub.14 H.sub.13     F.sub.2 N.sub.5 O.sub.2 S.sub.2 : 43.63 3.40 18.16        Found: 44.04     3.53 18.37      314 F F     ##STR89##      H CH.sub.3 132-135° C. Calcd. for C.sub.15 H.sub.13 F.sub.2     N.sub.5 O.sub.3 S:Found: 47.2447.15 3.443.58 18.3618.11  315 F F     CH.sub.2 OCH.sub.2 CH.sub.2 OCH.sub.3 H CH.sub.3 127-131° C.     Calcd. for C.sub.16 H.sub.17 F.sub.2 N.sub.5 O.sub.4 S: 46.49 4.15 16.93            Found: 46.40 4.17 17.11 316 F F (CH.sub.2).sub.4 COOCH.sub.2     CH.sub.3 H CH.sub.3 96-100° C. Calcd. for C.sub.19 H.sub.21     F.sub.2 N.sub.5 O.sub.4 S: 50.33 4.67 15.44        Found: 49.70 4.61     15.57

                                      TABLE XLV                                   __________________________________________________________________________     ##STR90##                                                                    Cmpd.                                                                              R.sup.1                                                                          R.sup.2                                                                          R.sup.3                                                                          R.sup.4                                                                          Melting Point                                                                         Elemental Analysis                                   __________________________________________________________________________                             Analysis       C  H  N                               304  Cl Cl Me Me 198-205° C.                                                                    Calcd. for C.sub.13 H.sub.15 Cl.sub.2 N.sub.5                                 O.sub.2 S:     41.49                                                                            3.98                                                                             18.50                                                    Found:         41.27                                                                            3.81                                                                             18.28                           305  CF.sub.3                                                                         H  Me Me 74.5-84° C.                                                                    Exact mass calcd. for C.sub.14 H.sub.16 F.sub.3                               N.sub.5 O.sub.2 S: 375.0979                                                   Found:             375.0978                                                   Analysis       C  H  N                               306  Cl Cl H  Me 230-235° C.                                                                    Calcd. for C.sub.12 H.sub.13 Cl.sub.2 N.sub.5                                 O.sub.2 S:     39.89                                                                            3.32                                                                             19.39                                                    Found:         39.72                                                                            3.42                                                                             19.90                           __________________________________________________________________________

                                      TABLE XLVI                                  __________________________________________________________________________     ##STR91##                                                                                         Elemental Analysis                                       Cmpd.                                                                             R.sup.1                                                                          R.sup.2                                                                          R.sup.5                                                                           Melting Point                                                                        Analysis      C  H  N                                    __________________________________________________________________________    317 Cl H  Cl  232-234° C.                                                                   Calcd. for C.sub.13 H.sub.11 Cl.sub.2 N.sub.5                                 O.sub.4 S:    38.62                                                                            2.74                                                                             17.30                                              (decomp.)                                                                            Found:        38.39                                                                            2.83                                                                             16.70                                318 CF.sub.3                                                                         H  OCH.sub.3                                                                         205-210° C.                                                                   Calcd. for C.sub.15 H.sub.14 F.sub.3 N.sub.5 O.sub.5                          S:            41.57                                                                            3.26                                                                             16.16                                              (decomp.)                                                                            Found:        41.19                                                                            3.27                                                                             15.98                                319 Cl CH.sub.3                                                                         Cl  206-208° C.                                                                   Calcd. for C.sub.14 H.sub.13 CL.sub.2 N.sub.5                                 O.sub.4 S:    40.20                                                                            3.13                                                                             16.75                                              (decomp.)                                                                            Found:        39.89                                                                            3.09                                                                             16.58                                320 F  H  Cl  229-230° C.                                                                   Calcd. for C.sub.13 H.sub.11 ClFN.sub.5 O.sub.4                                             40.26                                                                            2.86                                                                             18.06                                              (decomp.)                                                                            Found:        39.87                                                                            2.86                                                                             17.83                                321 Br H  Cl  231-233° C.                                                                   Calcd. for C.sub.13 H.sub.11 BrClN.sub.5 O.sub.4                                            34.80                                                                            2.47                                                                             15.61                                              (decomp.)                                                                            Found:        34.41                                                                            2.02                                                                             15.48                                322 Cl H  CH.sub.3                                                                          204-206° C.                                                                   Calcd. for C.sub.14 H.sub.14 ClN.sub.5 O.sub.4                                              43.81                                                                            3.68                                                                             18.25                                              (decomp.)                                                                            Found:        43.62                                                                            3.63                                                                             18.38                                __________________________________________________________________________

                                      TABLE XLVII                                 __________________________________________________________________________     ##STR92##                                                                                         Elemental Analysis                                       Cmpd.                                                                             R.sup.1                                                                          R.sup.2                                                                          R.sup.5                                                                           Melting Point                                                                        Analysis      C  H  N  S                                 __________________________________________________________________________    323 Cl H  Cl  214-215° C.                                                                   Calcd. for C.sub.13 H.sub.11 Cl.sub.2 N.sub.5                                 O.sub.3 S:    40.21                                                                            2.84                                                                             18.04                                              (decomp.)                                                                            Found:        39.84                                                                            3.08                                                                             17.99                                324 CF.sub.3                                                                         H  OCH.sub.3                                                                         205-210° C.                                                                   Calcd. for C.sub.15 H.sub.14 F.sub.3 N.sub.5 O.sub.4                          S:            43.16                                                                            3.38                                                                             16.78                                              (decomp.)                                                                            Found:        42.92                                                                            3.44                                                                             16.88                                325 Cl CH.sub.3                                                                         Cl  239-242° C.                                                                   Calcd. for C.sub.14 H.sub.13 Cl.sub.2 N.sub.5                                 O.sub.3 S:    41.80                                                                            3.26                                                                             17.41                                                                            7.97                                            (decomp.)                                                                            Found:        41.35                                                                            3.19                                                                             17.42                                                                            8.15                              326 Cl H  F   246-247° C.                                                                   Calcd. for C.sub.13 H.sub.11 ClFN.sub.5 O.sub.3                                             42.00                                                                            2.98                                                                             18.84                                              (decomp.)                                                                            Found:        41.63                                                                            3.10                                                                             18.57                                327 CF.sub.3                                                                         H  H   181-183° C.                                                                   Calcd. for C.sub.14 H.sub.12 F.sub.3 N.sub.5 O.sub.3                          S:            43.41                                                                            3.12                                                                             18.08                                                                            8.28                                            (decomp.)                                                                            Found:        43.20                                                                            3.13                                                                             17.88                                                                            8.18                              328 F  H  F   226-235° C.                                                                   Calcd. for C.sub.13 H.sub.11 F.sub.2 N.sub.5 O.sub.3                          S:            43.94                                                                            3.12                                                                             19.71                                                                            9.02                                            (decomp.)                                                                            Found:        43.50                                                                            3.09                                                                             19.32                                                                            8.81                              __________________________________________________________________________

                                      TABLE XLVIII                                __________________________________________________________________________     ##STR93##                                                                                          Elemental Analysis                                      Cmpd.                                                                             R.sup.1                                                                          R.sup.2                                                                          R.sup.5                                                                           Melting Point                                                                         Analysis      C  H  N  S                                __________________________________________________________________________    329 Cl H  Cl  222-225° C.                                                                    Calcd. for C.sub.14 H.sub.13 Cl.sub.2 N.sub.5                                 O.sub.3 S:    41.80                                                                            3.26                                                                             17.41                                                                            7.97                                                   Found:        41.56                                                                            3.37                                                                             17.24                                                                            7.76                             330 CF.sub.3                                                                         H  OCH.sub.3                                                                         210-213° C.                                                                    Calcd. for C.sub.16 H.sub.16 F.sub.3 N.sub.5                                  O.sub.4 S:    44.54                                                                            3.74                                                                             16.24                                                                            7.43                                                   Found:        43.89                                                                            3.68                                                                             16.00                                                                            7.70                             331 Cl CH.sub.3                                                                         Cl  228-229° C.                                                                    Calcd. for C.sub.15 H.sub.15 Cl.sub.2 N.sub.5                                 O.sub.3 S:    43.28                                                                            3.63                                                                             16.83                                                                            7.70                                                   Found:        42.87                                                                            3.66                                                                             16.92                                                                            7.66                             332 Cl H  F   211-212° C.                                                                    Calcd. for C.sub.14 H.sub.13 ClFN.sub.5 O.sub.3                                             43.58                                                                            3.40                                                                             18.15                                                     Found:        43.36                                                                            3.41                                                                             18.01                               333 CF.sub.3                                                                         H  H   187-188° C.                                                                    Calcd. for C.sub.15 H.sub.14 F.sub.3 N.sub.5                                  O.sub.3 S:    44.88                                                                            3.52                                                                             17.45                                                                            7.99                                                   Found:        44.67                                                                            3.49                                                                             17.48                                                                            8.10                             334 F  H  H   208.5-210.5° C.                                                                Calcd. for C.sub.14 H.sub.13 F.sub.2 N.sub.5                                  O.sub.3 S:    45.52                                                                            3.55                                                                             18.96                                                                            8.68                                                   Found:        45.28                                                                            3.56                                                                             19.31                                                                            8.60                             335 F  CH.sub.3                                                                         F   192-195° C.                                                                    Calcd. for C.sub.15 H.sub.15 F.sub.2 N.sub.5                                  O.sub.3 S:    46.99                                                                            3.94                                                                             18.27                                                                            8.36                                                   Found:        46.76                                                                            3.96                                                                             18.10                                                                            8.19                             __________________________________________________________________________

                                      TABLE XLIX                                  __________________________________________________________________________     ##STR94##                                                                                        Elemental Analysis                                        Cmpd.                                                                             R.sup.1                                                                          R.sup.2                                                                         R.sup.5                                                                           Melting Point                                                                        Analysis      C  H  N  S                                  __________________________________________________________________________    336 Cl H Cl  300-304° C.                                                                   Calcd. for C.sub.13 H.sub.11 Cl.sub.2 N.sub.5 O.sub.2                         S.sub.2 :     38.61                                                                            2.72                                                                             17.32                                              (decomp.)                                                                            Found:        38.99                                                                            2.93                                                                             17.34                                 337 CF.sub.3                                                                         H OCH.sub.3                                                                         245-249° C.                                                                   Calcd. for C.sub.15 H.sub.14 F.sub.3 O.sub.3 S.sub.2                          :             41.56                                                                            3.26                                                                             16.16                                              (decomp.)                                                                            Found:        41.42                                                                            3.25                                                                             16.30                                 338 CF.sub.3                                                                         H H   193-200° C.                                                                   Calcd. for C.sub.14 H.sub.12 F.sub.3 N.sub.5 O.sub.2                          S.sub.2 :     41.68                                                                            3.00                                                                             17.36                                                                            15.90                                                  Found:        41.39                                                                            2.95                                                                             17.21                                                                            15.65                              339 NO.sub.2                                                                         H CH.sub.3                                                                          266-267° C.                                                                   Calcd. for C.sub.14 H.sub.14 N.sub.6 O.sub.4 S.sub.2                          :             42.63                                                                            3.58                                                                             21.31                                                                            16.26                                                  Found:        42.32                                                                            3.64                                                                             21.46                                                                            15.98                              __________________________________________________________________________

                                      TABLE L                                     __________________________________________________________________________     ##STR95##                                                                                         Elemental Analysis                                       Cmpd.                                                                             R.sup.1                                                                          R.sup.2                                                                          R.sup.5                                                                           Melting Point                                                                        Analysis      C  H  N  S                                 __________________________________________________________________________    340 CF.sub.3                                                                         H  OCH.sub.3                                                                         228-235° C.                                                                   Calcd. for C.sub.16 H.sub.16 N.sub.5 O.sub.3 S.sub.2                          :             42.95                                                                            3.60                                                                             15.65                                                     Found:        42.55                                                                            3.53                                                                             15.53                                341 CF.sub.3                                                                         H  H   202-202.5° C.                                                                 Calcd. for C.sub.15 H.sub.14 F.sub.3 N.sub.5 O.sub.2                          S.sub.2 :     43.16                                                                            3.38                                                                             16.78                                                                            15.36                                                  Found:        43.09                                                                            3.42                                                                             16.69                                                                            15.41                             342 Cl H  CH.sub.3                                                                          231-233° C.                                                                   Calcd. for C.sub.15 H.sub.16 ClN.sub.5 O.sub.2                                S.sub.2 :     45.16                                                                            4.04                                                                             17.56                                                                            16.07                                                  Found:        45.31                                                                            4.10                                                                             17.44                                                                            16.17                             343 F  CH.sub.3                                                                         F   233-235° C.                                                                   Calcd. for C.sub.15 H.sub.15 F.sub.2 N.sub.5 O.sub.2                          S.sub.2 :     45.16                                                                            3.78                                                                             17.52                                                                            16.03                                                  Found:        44.77                                                                            3.89                                                                             17.14                                                                            16.42                             __________________________________________________________________________

                                      TABLE LI                                    __________________________________________________________________________     ##STR96##                                                                                    Elemental Analysis                                            Cmpd.                                                                             R.sup.1                                                                         R.sup.5                                                                          Melting Point                                                                        Analysis         C  H  N  Cl S                                __________________________________________________________________________    344 Cl                                                                              Cl 306-308° C.                                                                   Calcd. for C.sub.11 H.sub.7 ClN.sub.5 O.sub.4 S.H.sub.2                       O:               39.90                                                                            3.35                                                                             16.60                                           (decomp.)                                                                            Found:           40.36                                                                            3.32                                                                             16.08                                  345 F Cl 240-242° C.                                                                   Calcd. for C.sub.11 H.sub.7 ClFN.sub.5 O.sub.4 S.H.sub.2                      O:               34.98                                                                            2.40                                                                             18.54                                           (decomp.)                                                                            Found:           33.87                                                                            2.36                                                                             18.01                                  346 Br                                                                              Cl 200-203° C.                                                                   Calcd. for C.sub.11 H.sub.7 ClBrN.sub.5 O.sub.4 S.H.sub.2                     O:               30.12                                                                            2.07                                                                             15.97                                           (decomp.)                                                                            Found:           28.65                                                                            2.09                                                                             16.21                                  347 Cl                                                                              CH.sub.3                                                                         >250°  C.                                                                     Calcd. for C.sub.12 H.sub.10 ClN.sub.5 O.sub.4 S.H.sub.2                      O:               38.56                                                                            3.24                                                                             18.74                                                                            9.29                                                                             8.58                                      (decomp.)                                                                            Found            38.13                                                                            2.97                                                                             18.32                                                                            9.58                                                                             8.54                             __________________________________________________________________________

                                      TABLE LII                                   __________________________________________________________________________     ##STR97##                                                                                           Elemental Analysis                                     Cmpd.                                                                             R.sup.1                                                                          R.sup.2                                                                          R.sup.5                                                                             Melting Point                                                                        Analysis         C  H  N  S                            __________________________________________________________________________    348 Cl H  Cl    217-221° C.                                                                   Calcd. for C.sub.12 H.sub.8 Cl.sub.3 N.sub.5                                  O.sub.2 S:       36.70                                                                            2.04                                                                             17.84                                                  Found:           36.69                                                                            2.13                                                                             17.93                           349 CF.sub.3                                                                         H  OCH.sub.2 CH.sub.3                                                                  212° C.                                                                       Calcd. for C.sub.15 H.sub.13 ClF.sub.3 N.sub.5                                O.sub.3 S:       41.34                                                                            3.01                                                                             16.07                                           (decomp.)                                                                            Found:           41.14                                                                            3.21                                                                             16.41                           350 F  CH.sub.3                                                                         F     185-187° C.                                                                   Calcd. for C.sub.13 H.sub.10 ClF.sub.2 N.sub.5                                O.sub.2 S.H.sub.2 O:                                                                           39.85                                                                            3.09                                                                             17.88                                                                            8.18                                         (decomp.)                                                                            Found:           39.98                                                                            2.87                                                                             17.52                                                                            8.02                         __________________________________________________________________________

                                      TABLE LIII                                  __________________________________________________________________________     ##STR98##                                                                                    Elemental Analysis                                            Cmpd.                                                                             R.sup.1                                                                         R.sup.5                                                                          Melting Point                                                                        Analysis      C  H  N                                         __________________________________________________________________________    351 Cl                                                                              Cl 184-210° C.                                                                   Calcd. for C.sub.11 H.sub.5 Cl.sub.4 N.sub.5 O.sub.2                                        31.98                                                                            1.22                                                                             16.96                                              (decomp.)                                                                            Found:        31.54                                                                            1.70                                                                             17.41                                     352 Cl                                                                              CH.sub.3                                                                         222-224° C.                                                                   Calcd. for C.sub.12 H.sub.8 Cl.sub.3 N.sub.5 O.sub.2                                        36.71                                                                            2.05                                                                             17.84                                                     Found:        37.05                                                                            2.04                                                                             17.73                                     __________________________________________________________________________

The compounds of the present invention are highly effective herbicideswhen applied to the locus of vegetation, herein defined as encompassingpre-emergent (soil) applications as well as post-emergent (foliar)applications. They have utility for broad spectrum pre- and/orpost-emergence weed control in areas where complete vegetation controlis desired. Certain of these compounds are effective for the control ofnutsedge (cyperus spp.). The subject compounds are also useful forselective pre- and/or postemergence weed control in crops such as wheatcorn, soybeans, rice, and cotton. While none of the compounds areselective for use in all crops, by all methods of application, and atall rates of application, each is active as a herbicide and most areselective for use in one or more crops at some application rates and bysome methods of application. The data provided herein in the examplescan be used as a guide in choosing appropriately selective compoundsfrom the compounds of Formulae I and II, appropriate applicationmethods, and appropriate application rates for controlling unwantedvegetation in various crops. It is well within the skill of those in theart to select appropriate compounds of Formula I and II not mentioned inthe examples using the information herein and routine procedures.

Certain of the compounds of Formula I, notably those wherein X and Zrepresent C₁ -C₄ alkyl, are resistant to degradation in the environmentand, therefore, have limited utility as selective herbicides in cropswhere crop rotation programs are practiced except where the soil andclimate are especially favorable for degradation. These compounds, onthe other hand, are particularly useful as industrial herbicides wheremulti-year control is desired.

For all such uses, unmodified active ingredients of the presentinvention can be employed. However, the present invention embraces theuse of a herbicidally-effective amount of the active ingredients incomposition form with an inert material known in the art as anagricultural adjuvant or carrier in solid or liquid form. Such adjuvantsor carriers must not be phytotoxic to valuable crops particularly at theconcentration employed in applying the composition in attemptingselective weed control in the presence of crops. If weed control isdesired in the absence of crops, it is generally sufficient to employadjuvants or carriers which do not leave a persistent phytotoxicresidue.

Thus, for example, an active ingredient can be dispersed on afinely-divided solid and employed therein as a dust. Also, the activeingredients, as liquid concentrates or solid compositions comprising oneor more of the active ingredients can be dispersed in water, typicallywith aid of a wetting agent, and the resulting aqueous dispersionemployed as a spray. In other procedures the active ingredients can beemployed as a constituent of organic liquid compositions, oil-in-waterand water-in-oil emulsions or dispersions, with or without the additionof wetting, dispersing, or emulsifying agents.

Suitable adjuvants of the foregoing type are well known to those skilledin the art. The methods of applying the solid or liquid herbicidalformulations similarly are well known to the skilled artisan.

Organic solvents that can be employed include toluene, xylene, kerosene,diesel fuel, fuel oil, and petroleum naphtha, ketones such as acetone,methylethyl ketone and cyclohexanone, chlorinated hydrocarbons such astrichloroethylene, and perchloroethylene, esters such as ethyl acetate,amyl acetate and butyl acetate, ethers, e.g., ethylene glycol monomethylether and diethylene glycol monomethyl ether, alcohols, e.g., methanol,ethanol, isopropanol, amyl alcohol, ethylene glycol, propylene glycol,butylcarbitol acetate and glycerine. Mixtures of water and organicsolvents, either as emulsions or solutions, can be employed.

The active ingredients of the present invention can also be applied asaerosols, e.g., by dispersing them by means of a compressed gas such asone of the fluorocarbons or one of its hydrocarbon successors.

The active ingredients of the present invention can also be applied withsolid adjuvants or carriers such as talc, pyrophyllite, synthetic finesilica, attapulgus clay, kieselguhr, chalk, diatomaceous earth, lime,calcium carbonate, bentonite, Fuller's earth, cotton seed hulls, wheatflour, soybean flour, pumice, tripoli, wood flour, walnut shell flour,redwood flour and lignin.

As stated, it is frequently desirable to incorporate a surface-activeagent in the compositions of the present invention. Such surface-activeor wetting agents are advantageously employed in both the solid andliquid compositions. The surface-active agent can be anionic, cationicor nonionic in character.

Typical classes of surface-active agents include alkyl sulfonate salts,alkylaryl sulfonate salts, alkylaryl polyether alcohols, fatty acidesters of polyhydric alcohols and the alkylene oxide addition productsof such esters, and addition products of long-chain mercaptans andalkylene oxides. Typical examples of such surface-active agents includethe sodium alkylbenzene sulfonates having 10 to 18 carbon atoms in thealkyl group, alkyl phenol ethylene oxide condensation products, e.g.,p-isooctylphenol condensed with 20 ethylene oxide units, soaps, e.g.,sodium stearate and potassium oleate, sodium salt of propylnaphthalenesulfuric acid, di(2-ethylhexyl)ester of sodium sulfosuccinic acid,sodium lauryl sulfate, sodium decyl sulfonate, sodium salt of thesulfonated monoglyceride of coconut fatty acids, sorbitan sesquioleate,lauryl trimethyl ammonium chloride, octadecyl trimethyl ammoniumchloride, polyethylene glycol lauryl ether, polyethylene glycol estersof fatty acids and rosin acids, e.g., Ethofat® 7 and 13, sodiumN-methyl-N-oleyl taurate, sodium dibutylnaphthalene sulfonate, sodiumlignin sulfonate, polyethylene glycol stearate, sodium dodecyl benzenesulfonate, tertiary dodecyl polyethylene glycol thioether (nonionic218), long-chain ethylene oxide-propylene oxide condensation productse.g., Pluronic® 61 (molecular weight about 1000), polyethylene glycolester of tall oil acids, sodium octophenoxyethoxyethyl sulfate,tris(polyoxyethylene)sorbitan monostearate (Tween® 60), and sodiumdihexylsulfosuccinate.

The herbicidally effective concentration of the active ingredients insolid or liquid compositions generally is from about 0.00003 to about 95percent by weight or more. Concentrations from about 0.05 to about 50percent by weight are often employed. In compositions to be employed asconcentrates, the active ingredient can be present in a concentrationfrom about 5 to about 98 weight percent, preferably 15-50 weightpercent. The active ingredient compositions can also contain othercompatible additaments, for example, phytotoxicants, plant growthregulants, pesticides and the like and can be formulated with solidparticulate fertilizer carriers such as ammonium nitrate, urea and thelike.

In further embodiments, the compounds of the present invention orcompositions containing the same, can be advantageously employed incombination with one or more additional pesticidal compounds. Suchadditional pesticidal compounds may be insecticides, nematocides,miticides, arthropodicides, herbicides, fungicides or bactericides thatare compatible with the compounds of the present invention in the mediumselected for application. In such embodiments, the pesticidal compoundis employed as a supplemental toxicant for the same or for a differentpesticidal use or as an additament.

The compounds of the present invention are particularly useful incombination with other herbicides including, for example, thesubstituted urea herbicides such as3-(3,4-dichlorophenyl)-1,1-dimethylurea,3-(3,4-dichlorophenyl)-1-methoxy-1-methylurea (Lorox®) and1,1-dimethyl-3-(α,α,α-trifluoro-m-tolyl)urea (Cotoran®); the triazinessuch as 2-chloro-4-(ethylamino)-6-(isopropylamino)-s-triazine and2-chloro-4-(1-cyano-1-methylethylamino)-6-ethylamino-s-triazine(Bladex®); the uracils such as 5-bromo-3-sec-butyl-6-methyluracil;N-(phosphonomethyl)glycine; the phenoxies such as2,4-dichlorophenoxyacetic acid; picolinic acids such as4-amino-3,5,6-trichloropicolinic acid (Tordon®) and3,6-dichloropicolinic acid (Lontrel®); 4-chloro-2-butynyl-3-chlorophenylcarbamate (Carbyne®); diisopropylthiocarbamic acid; ester with2,3-dichloroallyl alcohol (Avadex®); diisopropylthiocarbamic acid, esterwith 2,3,3-trichloroallyl alcohol (Avadex® BVD);ethyl-N-benzoyl-N-(3,4-dichlorophenyl)-2-aminopropionate (Suffix®);1,2-dimethyl-3,5-diphenylpyrazolium methylsulfate (Avenge®); methyl(2-[4-(2,4-dichlorophenoxy)phenoxy]propanoate) (Hoelon®); butyl2-[4-[(5-(trifluoromethyl)-2-pyridinyl)oxy]phenoxy]propanoate(Fusilade®); esters of2-[4-[(3-chloro-5-trifluoromethyl)-2-pyridinyl)oxy]phenoxy]propionicacid; 4-amino-6-tert-butyl-3-(methylthio)-1,2,4-triazin-5-(4H)-one(Lexone®); 3-isopropyl-1H-2,1,3-benzothiadiazin-(4)-3H-one 2,2-dioxide;α,α,α-trifluoro-2,6-dinitro-N,N-dipropyl-p-toluidine;1,1'-dimethyl-4,4'-bipyridinium ion;2-chloro-2',6'-diethyl(methoxymethyl)acetanilide; and2-[1-(ethoxyimino)butyl]-5-[(2-ethylthio)propyl]-3-hydroxy-2-cyclohexen-1-one(Poast®).

The rates of application for compounds of the invention are determinedby a number of factors including the active ingredient being applied,the particular action desired (e.g., general or selective control), theplant species to be modified and the stage of growth thereof, the partof the plant to be contacted with the toxic active ingredient, theformulation selected, weather and climate, etc. Thus, it is to beunderstood that all of the active ingredients of the present inventionand compositions containing the same may not be equally effective atsimilar concentrations or against the same plant species. Innon-selective preemergence and foliar treatments, the active ingredientsof the invention are usually applied at an approximate rate of fromabout 0.01 to about 10 pounds/acre. In pre- and postemergence operationsfor selective uses, a dosage of about 0.01 to about 10 pounds/acre isgenerally applicable, a rate of 0.01 to 4 pounds/acre being preferred.

The following example illustrates the effect of the compounds of thisinvention applied postemergently.

Plant species in this and other tests were the following:

    ______________________________________                                        Common Name         Scientific Name                                           ______________________________________                                        A.     cotton           Gossypium spp.                                        B.     rape             Brassica napus                                        C.     soybean          Glycine max.                                          D.     sugar beet       Beta saccharifera                                     E.     cocklebur        Xanthium spp.                                         F.     jimsonweed       Datura stramonium                                     G.     annual morning glory                                                                           Ipomoea spp.                                          H.     pigweed          Amaranthus spp.                                       I.     velvetleaf       Abutilon theophrasti                                  J.     corn             Zea mays                                              K.     rice             Oryza sativa                                          L.     sorghum          Sorghum vulgare                                       M.     wheat            Triticum aestivum                                     N.     barnyardgrass    Echinochloa crusgalli                                        (watergrass)                                                           O.     crabgrass        Digitaria spp.                                        P.     yellow foxtail   Setaria lutescens                                     Q.     johnson grass    Sorghum halepense                                     R.     wild oats        Avena fatua                                           S.     sprangletop      Leptochloa filiformis                                 T.     yellow nutsedge  Cyperus esculentus                                    ______________________________________                                    

EXAMPLE 118

In representative operations, each compound to be utilized in a seriesof tests is dissolved in acetone to one-half of the final volume (twicethe final concentration) to be used and the acetone solution in eachcase is admixed with an equal volume of water containing 0.1 percent byweight of surface active material. The compositions, generally in thenature of an emulsion, were employed to spray separate respective plantspecies which had been grown to a 2-4 leaf stage in soil or goodnutrient content in a greenhouse. Sufficient amounts were employed toprovide various application rates as listed in the table. The variousbeds were positioned side by side and exposed to substantially identicalconditions of temperature and light. Each bed was maintained so as toprevent any interaction with test compounds in different seed beds.Other plants were left untreated to serve as controls. After treatment,the plants were maintained for about two weeks under greenhouseconditions conducive for good plant growth and watered as necessary. Thespecific plant species test compound and dosage and the percentpost-emergent control obtained at one or more dosages tested are setforth in the table below. Control refers to the reduction in growthcompared to the observed result of the same untreated species.

      POSTEMERGENT CONTROL OF PLANT SPECIES Dosage Plant Species Compound     (ppm) A B C D E F G H I J K L M N O P Q R T       1 15.6 90 100 95 -- 95 60 85 98 100 100 98 100 100 95 -- 95 98 90 70 2     1000 10 50 40 90 80 90 10 0 50 0 20 0 0 0 0 0 90 0 0 4 500 10 40 40 70     40 60 0 0 60 0 40 40 0 0 20 0 80 0 0 6 500 60 80 70 90 90 30 80 30 90 0     20 80 0 35 20 0 80 0 90 7 500 -- 90 55 100 100 20 90 60 65 0 15 65 0 35     0 25 50 0 65 8 500 -- 90 75 95 90 90 70 50 75 20 40 70 10 70 10 25 90 0     60  62.5 -- 60 40 60 70 15 35 40 20 0 30 20 0 5 0 10 20 0 0 9 1000 50 60     65 80 90 90 20 80 40 0 30 90 0 20 40 0 30 0 40 10 2000 15 30 50 75 90 0     0 100 15 10 -- 10 0 0 0 0 0 0 60  500 0 10 20 60 15 0 0 20 0 0 -- 0 0 0     0 0 0 0 0 12 500 -- 100 80 95 100 70 100 100 95 10 25 75 0 80 25 20 55 0     90  125 -- 95 80 95 100 20 60 90 75 0 10 60 0 10 0 0 25 0 40  15.6 -- 75     60 65 90 0 20 70 0 0 0 0 0 0 0 0 0 0 0 13 250 95 100 95 100 100 90 90     100 95 15 15 90 0 90 20 70 90 0 90  62.5 95 100 95 95 100 50 90 100 80 0     0 80 0 100 0 50 85 0 75  15.6 60 90 85 90 100 30 85 70 70 0 0 80 0 0 0 0     70 0 0 14 1000 20 -- 25 90 80 0 10 60 0 0 30 0 0 0 0 0 0 0 0 15 1000 --     70 25 40 80 0 70 40 60 0 35 40 0 0 0 0 0 0 10 17 1000 20 95 15 15 10 0 0     60 85 30 0 60 10 0 15 10 85 0 0  500 15 70 15 10 10 0 0 50 70 20 0 40 0     0 0 20 60 0 0 19 1000 90 90 90 100 90 95 40 100 80 0 0 50 0 20 20 0 65 0     85 21 1000 90 100 70 95 95 0 45 80 30 0 20 30 0 0 0 0 20 0 80 22 250 100     100 95 100 100 100 100 100 95 25 50 90 10 100 90 100 100 20 85  62.5 95     100 90 100 100 95 80 100 95 15 20 90 0 100 75 90 100 0 80  15.6 85 95 90     90 90 80 75 95 90 0 0 75 0 100 0 95 85 0 40 24 1500 40 90 40 70 90 -- 0     -- 50 0 20 10 0 0 -- -- 10 0 0 25 250 100 100 90 100 100 100 80 100 95     70 60 85 0 9090 95 100 20 80  62.5 90 100 80 100 100 100 35 100 60 40 10     80 0 70 70 90 90 0 60  15.6 30 -- 70 90 90 80 20 100 40 20 0 60 0 20 0     70 75 0 0 26 500 100 100 95 100 100 100 90 100 100 80 80 90 30 100 90 90     100 0 90  125 100 100 85 100 100 100 85 100 90 80 40 85 0 100 80 75 95 0     80  31.25 90 100 80 95 90 60 75 100 40 20 0 50 0 100 20 30 60 0 80 30     500 0 40 30 0 40 0 60 0 40 0 20 0 0 0 0 0 0 0 0 31 125 90 100 95 100 90     100 60 85 90 40 0 90 0 40 80 90 100 0 75  31.25 75 95 90 90 75 80 40 80     95 50 0 80 0 20 75 80 100 0 80  7.8 60 60 75 100 60 60 0 55 85 30 0 50 0     0 0 60 80 0 50 32 500 20 0 15 30 15 60 0 0 50 0 10 0 30 0 10 10 95 0 0     250 30 0 15 0 0 30 0 0 40 0 20 0 0 0 0 0 80 0 0 33 500 50 60 40 40 60 40     60 10 80 25 0 80 0 0 0 0 60 0 10 34 500 70 100 90 100 100 90 75 100 100     0 0 60 0 0 0 0 20 0 60 35 500 0 70 70 80 95 30 40 90 0 0 0 20 -- 0 0 0 0     0 0 38 62.5 80 98 90 100 98 60 80 98 98 0 0 20 0 10 10 95 90 0 30  15.6     10 98 70 98 95 50 50 80 40 0 0 0 0 0 5 80 50 0 10 39 62.5 98 98 98 98     100 90 98 100 98 0 0 65 0 50 70 97 90 0 40  15.6 80 98 98 98 95 90 95 95     98 0 0 80 0 40 0 90 80 0 20  3.9 40 95 40 98 90 40 70 70 40 0 0 5 0 0 0     80 0 0 0 40 1000 25 90 25 90 80 60 20 75 20 0 0 20 0 0 0 0 0 0 20 41     4000 30 -- -- -- -- -- 70 -- 98 -- -- -- -- 80 40 40 -- -- 95 43 2000 0     20 15 0 0 0 0 -- 0 0 0 0 0 0 25 0 20 0 0 44 250 40 80 75 80 85 20 75 90     80 0 0 20 0 0 0 40 0 0 60 45 500 0 70 60 70 25 0 10 -- 50 0 50 0 0 0 0 0     0 0 0 46 31.3 95 98 98 98 98 95 98 100 98 15 0 0 0 0 10 80 50 0 40  7.8     80 95 98 98 98 80 98 100 98 15 0 0 0 0 0 0 0 0 20  1.9 60 98 95 95 95 30     90 90 95 15 0 0 0 0 0 0 0 0 10 47 62.5 70 90 98 100 98 20 98 90 98 0 0 0     0 0 0 0 0 0 10 48 500 10 75 55 70 70 30 60 -- 40 0 0 0 0 0 0 0 0 0 0 49     250 90 100 95 100 100 100 95 90 100 0 10 80 0 90 80 95 80 20 90  62.5 95     100 95 100 100 100 95 80 100 0 0 70 0 80 60 90 100 0 90 50 62.5 98 100     100 100 98 98 98 98 100 93 97 90 0 95 95 99 97 90 90  15.6 90 100 98 90     98 90 80 90 100 70 97 50 0 80 80 97 95 10 80 51 62.5 98 98 98 98 100 95     98 90 100 40 40 90 0 20 0 93 95 10 80  7.8 30 70 80 95 95 60 90 20 70 0     0 50 0 0 0 0 20 0 70 52 2000 70 10 70 50 70 0 -- 0 0 0 0 0 0 0 0 0 0 0 0     53 62.5 90 100 98 100 100 98 90 100 100 0 10 90 0 70 50 95 97 0 60  15.6     60 98 98 98 98 98 90 100 98 0 0 90 0 65 20 97 93 0 80 54 62.5 98 98 98     100 98 90 98 98 98 30 40 93 20 50 30 95 97 15 30  7.8 60 98 80 98 98 40     40 90 50 0 0 25 0 0 0 25 60 0 0 55 125 25 70 15 95 80 25 20 20 20 0 0 0     0 0 0 0 0 0 0 56 62.5 85 95 90 100 99 85 80 95 90 0 0 55 0 0 40 75 95 0     15 57 125 20 95 10 85 80 0 0 0 -- 0 0 70 -- 0 0 0 85 0 0 58 125 90 100     95 100 100 95 95 100 100 85 60 95 60 95 90 90 100 -- 90  31.25 90 100 95     100 100 95 90 100 95 75 50 90 0 90 95 90 95 -- 90 59 250 0 70 10 40 75     50 0 0 -- 0 0 0 0 0 0 0 0 0 0 60 2000 60 -- 15 -- -- 50 80 100 80 -- 0     10 0 -- 0 0 -- -- 15 61 125 40 75 90 90 30 75 5 60 40 0 15 0 0 0 70 25     35 0 5 62 125 40 80 90 70 80 75 65 75 80 0 15 45 0 0 10 10 80 0 15 63     62.5 90 90 90 90 95 95 80 90 90 0 10 60 0 50 40 65 60 0 60 64 125 100 99     90 100 -- 95 80 100 100 85 70 80 80 0 90 80 90 0 80 65 250 -- 85 75 60     -- 10 0 40 -- 70 0 70 0 50 70 90 90 0 15 66 1000 50 80 0 90 -- 0 0 95 30     0 0 20 0 0 30 0 80 0 0 67 1000 40 70 0 30 -- 0 0 100 30 0 0 0 0 0 20 20     0 0 0 68 1000 70 80 60 100 100 75 50 100 90 0 25 80 0 30 80 95 75 0 75     125 80 50 40 40 60 25 0 65 50 0 0 25 0 0 0 50 60 0 20 69 500 90 90 40     100 -- 90 80 100 85 90 0 80 0 80 80 90 95 0 80  62.5 75 80 5 40 -- 50 60     100 50 40 0 40 0 0 0 70 30 0 60 70 250 90 95 70 90 95 95 80 50 85 0 0 0     0 0 75 80 80 0 90 71 500 75 70 35 70 0 60 0 0 70 0 0 0 0 0 20 0 0 0 0 72     62.5 100 100 85 50 100 90 85 70 100 0 35 50 0 50 0 40 70 0 85 73 125 0     50 50 30 80 70 20 40 50 0 0 0 0 0 0 0 0 0 25 74 500 70 100 80 100 100 90     80 70 100 0 0 80 0 70 0 60 50 0 95 75 125 25 65 40 0 75 40 0 0 100 0 20     0 0 10 0 0 0 0 5 76 125 80 95 90 90 90 100 90 100 100 40 80 40 20 35 65     98 60 10 95  31.25 60 95 80 60 70 50 80 80 98 30 70 50 0 30 50 85 30 0     80 77 125 80 100 90 80 85 100 95 100 100 10 30 0 0 40 20 98 20 0 15     15.6 50 -- 75 20 50 80 50 20 80 0 15 0 0 0 0 40 20 0 15 78 125 75 95 90     85 40 0 0 100 90 0 50 50 0 10 10 50 0 0 75 79 2000 80 90 70 90 75 85 15     30 75 0 0 75 0 10 0 0 60 25 0 81 2000 50 -- 10 0 -- 20 0 30 40 0 0 0 0 0     0 0 0 0 40 82 500 85 100 85 95 85 90 85 100 85 0 0 0 0 0 0 0 0 0 0 83     62.5 50 60 10 60 20 0 0 0 30 0 0 0 0 0 0 0 0 0 0 84 2000 30 100 40 100     -- -- 0 100 98 0 0 0 0 0 0 0 0 0 30 85 62.5 70 -- 80 100 70 70 75 100 80     30 0 40 0 50 50 75 0 0 60  7.8 50 -- 80 100 55 80 55 100 80 0 0 20 0 0 0     70 0 0 50 86 125 50 80 80 100 60 -- 0 100 65 0 0 40 0 30 0 70 0 0 20 87     250 50 80 75 100 40 50 40 70 60 0 0 20 0 0 0 0 0 20 30 89 2000 50 -- 35     80 70 85 20 100 90 0 10 30 0 0 50 40 0 0 50 90 500 0 70 50 -- 75 70 30     100 50 0 0 0 0 0 -- 70 20 0 0 91 62.5 100 100 90 100 100 100 90 100 100     0 0 0 0 0 0 95 20 0 95 92 62.5 25 50 80 0 -- 90 80 60 50 40 0 0 0 0 0 0     0 0 0 93 500 0 70 90 70 80 80 0 70 20 0 0 0 0 0 0 0 0 0 15 94 2000 0 60     85 100 80 70 0 70 70 0 0 25 0 20 0 0 0 0 80 97 1000 70 90 70 90 90 20 50     100 80 0 30 55 0 60 0 70 60 00 98 4000 60 -- -- -- -- 60 100 90 -- -- --     -- -- 0 30 98 -- 0 0 99 2000 25 80 60 65 0 0 0 50 20 0 20 0 0 0 0 0 0 0     0 101 2000 40 -- 50 100 50 80 0 100 35 0 30 0 0 20 0 80 0 0 50 103 4000     0 -- -- -- -- -- 100 100 80 -- -- -- -- 0 0 0 -- 0 -- 104 125 65 95 90     100 85 100 100 100 100 100 100 100 80 100 100 100 100 80 80  3.9 35 85     80 100 70 75 90 100 90 85 85 95 50 100 -- 100 95 50 60 105 500 35 40 95     90 100 60 70600 80 20 0 0 20 0 -- 0 0 0 106 500 30 40 90 0 90 0 80 40 0     90 30 40 20 30 0 0 90 30 0  250 0 20 90 0 40 0 80 20 0 50 10 30 0 0 0 0     80 20 0 107 1000 0 50 85 15 80 0 0 40 25 0 0 40 0 0 0 0 75 0 0 108 500     70 40 75 70 80 30 10 0 90 80 0 80 60 100 0 0 100 0 35  125 60 25 75 35     70 15 0 0 20 85 0 90 0 100 0 0 80 0 5 111 250 25 90 70 90 95 50 80 70 85     0 0 10 0 0 0 0 50 0 60 112 125 0 90 85 90 95 65 80 60 85 0 0 60 0 0 0 0     15 0 40 113 250 30 70 15 90 90 50 80 70 75 0 0 50 0 0 0 0 10 0 60 114     1000 25 95 40 100 100 100 80 -- 90 0 0 25 85 90 0 40 30 0 75  62.5 0 50     25 0 20 60 0 0 60 0 0 0 0 0 0 0 0 0 0 116 250 100 -- 45 100 95 90 25 95     90 0 0 0 0 10 0 65 0 0 50 117 500 90 100 35 100 100 100 80 75 100 0 0 60     0 0 0 65 75 0 25  62.5 60 75 0 80 90 90 50 40 50 0 0 15 0 0 0 40 25 0 0     118 500 0 80 0 100 100 100 70 70 80 0 0 0 -- 0 60 20 0 0 70 119 500 0     100 0 50 70 90 30 0 70 30 0 0 0 0 0 0 80 0 40 120 250 100 90 98 80 98 90     100 100 80 0 98 35 0 0 0 70 0 0 70 133 4000 20 -- -- -- -- -- 40 100 40     -- -- -- -- 0 0 0 -- 0 0 135 2000 0 50 40 90 75 750 -- 75 0 0 10 0 0 0 0     0 0 0 136 500 30 80 30 80 98 30 40 90 70 0 0 0 0 0 0 0 0 0 0 137 1000 --     -- 50 100 70 100 100 100 80 0 50 50 25 75 98 80 80 50 50  62.5 40 -- 35     90 30 70 50 100 75 0 30 0 0 60 20 75 20 0 20 138 125 70 100 40 80 80 80     50 100 85 0 80 50 30 80 60 85 70 0 0  31.2 40 98 0 70 70 50 0 100 65 0 0     0 0 20 0 85 70 0 0 139 125 60 98 50 100 100 85 90 100 100 0 0 65 20 0 20     75 80 0 40 140 125 90 100 65 100 100 95 100 100 90 0 100 95 30 80 80 80     100 50 35  31.2 95 100 50 100 100 80 50 100 85 0 55 70 0 20 50 98 90 0 0     141 125 60 98 80 100 70 98 90 100 98 0 80 65 50 80 95 100 80 70 80  31.2     60 100 75 100 65 80 80 100 95 0 80 55 0 75 0 80 80 0 60 142 2000 80 75     50 95 100 80 75 -- 35 0 0 75 0 0 50 80 80 0 0 143 62.5 98 100 60 100 95     50 100 100 0 70 93 0 93 60 97 97 97 0 90  15.6 98 98 20 100 90 20 100     100 0 50 30 0 35 50 80 80 80 0 70  3.9 80 70 0 98 40 0 60 90 0 0 0 0 0     10 70 70 0 0 0 144 62.5 80 95 15 100 99 99 80 100 100 0 75 80 0 80 100     95 100 0 85  7.8 55 70 0 100 85 70 35 95 95 0 15 25 0 50 40 90 10 0 55     145 62.5 75 90 35 100 100 90 95 100 100 0 -- 80 0 15 25 75 75 0 20  7.8     50 65 0 95 95 55 65 100 75 0 -- 45 0 0 0 0 65 0 0 146 62.5 50 95 85 100     100 95 95 100 100 15 90 75 0 95 95 95 90 -- 85  3.9 20 50 5 70 90 75 60     75 75 0 40 10 0 20 0 75 25 -- 55 147 15.6 80 90 45 100 -- 90 80 100 100     0 0 0 0 0 20 80 40 0 80  3.9 25 70 5 100 -- 60 60 90 90 0 0 0 0 0 0 0 0     0 15 148 25 75 -- 0 ---- 80 0 100 90 -- -- 70 0 -- 60 95 -- -- 90 149     2000 0 -- 0 -- -- 0 0 100 10 -- -- 0 0 -- 0 90 -- -- 0 150 125 10 70 0     90 90 90 35 70 80 0 0 0 0 10 0 80 25 0 65 151 62.5 95 100 25 -- 100 100     95 100 95 0 25 40 0 80 0 85 -- 0 95  15.6 80 75 0 -- 100 100 90 100 95 0     0 0 0 30 0 85 -- 0 90 152 125 100 100 45 100 100 100 100 100 100 0 50 80     0 100 0 100 90 0 95  7.8 90 90 0 90 80 80 85 90 100 0 0 40 0 55 0 90 65     0 90 153 125 90 100 35 100 100 100 85 100 100 0 50 80 0 90 25 100 80 0     90  7.8 70 100 0 100 60 70 55 40 90 0 0 20 0 70 0 55 0 0 80 154 62.5 40     90 0 80 95 90 50 20 90 0 25 0 0 0 0 0 0 0 30 155 125 90 100 20 100 100     95 85 100 100 0 20 75 10 15 0 75 75 0 95  15.6 75 90 0 95 50 80 15 80 95     0 0 15 0 0 0 50 10 0 80 156 31.25 75 90 0 100 90 100 85 100 100 0 40 20     0 0 0 0 10 0 85 157 15.6 70 90 0 80 50 90 40 70 90 0 0 80 0 0 0 75 80 0     0 158 31.25 75 95 20 100 40 90 60 90 95 0 0 50 0 10 0 70 50 0 0  7.8 45     80 10 90 0 80 10 40 65 0 0 0 0 0 0 25 0 0 0 159 125 100 100 25 100 100     100 100 100 100 0 35 75 -- 100 0 75 100 0 90  15.6 50 100 0 100 70 100     70 70 95 0 15 50 -- 50 0 60 40 0 10 160 62.5 65 80 65 100 75 -- 60 100     100 0 0 50 0 30 50 70 30 0 100 161 250 80 85 40 80 65 100 75 100 60 15 0     65 0 15 30 50 10 0 50 162 62.5 40 80 0 -- 10 70 20 95 80 0 40 55 0 15 30     70 0 0 0 163 500 0 70 0 0 40 70 0 90 20 0 0 0 0 0 0 50 0 0 0 164 125 90     95 30 100 80 95 80 100 100 0 0 85 0 65 0 70 75 0 70  31.25 60 90 0 100     50 50 10 100 90 0 0 15 0 0 0 60 0 0 85 165 62.5 70 70 30 90 50 50 60 100     80 0 0 0 0 50 0 70 20 0 80  15.6 45 40 0 70 20 50 40 80 45 0 0 0 0 20 0     50 25 0 60 166 62.5 60 65 55 70 70 60 75 100 90 80 0 0 0 80 80 85 100 30     70  15.6 40 40 40 60 20 50 50 100 80 0 0 0 0 65 0 50 0 0 60 168 62.5 60     -- 80 --70 70 98 100 90 0 0 0 0 0 90 80 -- 0 80  15.6 20 90 80 -- 50 --     75 100 60 0 0 0 0 0 0 75 -- 0 -- 169 125 50 80 0 80 30 70 0 70 65 0 0 20     0 0 0 0 0 0 0 170 500 50 -- 30 95 25 90 70 100 90 25 35 25 0 75 60 80 85     80 98  125 50 100 0 90 15 80 60 100 80 0 30 50 0 40 60 70 80 40 -- 171     2000 60 30 -- 90 0 50 0 0 50 0 -- 0 0 0 -- 0 0 0 0 172 1000 40 80 50 80     20 70 20 100 70 0 0 0 0 0 0 40 0 0 50 173 125 0 80 40 100 0 -- 0 80 0 0     25 0 -- 0 -- 20 50 0 0 174 62.5 80 -- 70 90 80 85 100 100 100 20 70 70     25 80 98 80 85 85 90  7.8 100 80 50 90 40 80 70 100 90 0 30 20 0 40 20     80 40 40 100 175 62.5 100 -- 40 100 100 100 100 100 100 0 30 80 0 100     100 100 80 40 20 176 250 0 95 65 80 0 80 50 100 80 0 0 20 0 0 0 20 100 0     0 177 62.5 90 98 80 90 98 85 80 100 100 50 98 90 50 100 80 98 98 60 65     7.8 50 85 60 80 50 40 80 100 100 0 80 50 0 80 50 95 80 20 45 178 250 50     90 50 80 90 85 35 -- 80 0 75 0 0 0 0 0 0 0 0 179 62.5 0 50 10 75 50 15 0     0 0 0 0 0 0 0 0 0 0 0 0 180 500 100 100 100 100 100 100 90 -- 100 0 10     50 0 10 90 75 20 0 90  125 95 100 90 100 100 100 90 -- 100 0 0 40 0 0 40     60 0 0 40 181 125 90 99 95 90 80 -- 80 100 95 0 0 50 0 0 0 95 40 0 0 182     125 90 98 95 -- 100 98 60 100 98 0 0 0 0 0 20 95 20 30 20 183 125 65 95     0 98 50 90 0 95 90 0 0 20 0 0 20 20 20 0 0 184 125 95 100 90 -- 90 100     85 100 100 0 0 50 0 0 20 80 30 100 50 185 62.5 90 98 -- 95 90 90 50 --     90 0 -- 50 0 0 -- -- 20 0 0 186 4000 100 -- -- -- -- -- 80 100 100 -- --     -- -- 50 70 90 -- 30 90 187 125 40 -- 90 85 80 80 80 98 90 0 0 0 0 0 0     70 0 0 70 188 125 90 80 95 85 60 80 100 100 90 0 50 50 20 70 80 80 60 70     70 189 125 80 100 85 100 25 80 80 90 90 0 25 50 0 70 50 70 40 25 70 190     125 98 80 85 100 80 -- 20 100 85 15 0 40 0 0 20 85 40 0 0 191 125 60 100     80 95 70 100 80 98 98 0 80 70 30 100 60 100 90 65 30  31.2 40 100 80 80     20 80 80 50 70 0 50 70 0 75 20 100 80 50 30 192 125 80 100 20 100 -- 90     90 100 90 0 0 0 0 0 0 40 0 0 98  31.25 40 90 0 100 -- 80 40 100 20 0 0 0     0 0 0 0 0 0 90 193 250 80 100 40 100 30 100 80 100 98 0 20 0 0 60 60 90     75 0 65 194 250 50 100 60 100 70 100 10 100 95 0 0 10 0 0 30 80 25 0 70     195 250 80 90 65 100 25 85 80 98 100 0 0 0 0 20 20 80 30 0 60 196 250 70     100 40 100 90 100 100 100 100 0 0 30 10 20 70 80 40 10 70 197 250 80 85     40 80 65 100 75 100 60 15 0 65 0 15 30 50 10 0 50 198 2000 60 100 0 90 0     0 50 30 90 0 0 0 0 0 0 0 0 0 0 199 62.5 40 100 90 90 -- 40 10 98 80 0 0     0 0 0 0 0 0 0 0 200 62.5 0 95 35 95 -- 30 0 40 50 0 0 0 0 0 0 0 0 0 35     201 500 0 20 0 50 80 70 0 90 60 0 0 0 0 0 0 0 0 0 0 204 1000 70 60 15 60     -- 50 0 0 90 0 0 10 0 0 0 0 0 0 10 205 250 -- 75 60 95 -- 60 40 100 --     45 0 80 0 40 95 95 100 0 60 206 250 40 100 20 100 100 90 98 100 98 0 0 0     0 0 20 90 80 0 80 207 1000 90 100 25 100 95 95 50 30 100 0 0 0 0 20 0 20     40 0 70 208 62.5 80 100 65 95 65 95 50 100 90 0 0 15 0 0 0 50 0 0 25 209     250 0 70 0 40 80 70 0 0 70 0 0 0 0 0 0 0 0 0 0 210 62.5 35 30 20 40 0 --     0 0 55 0 0 0 0 0 0 0 0 0 0 211 1000 20 -- 0 40 20 -- 0 75 60 0 0 10 0 0     0 0 25 0 0 212 2000 0 -- 55 98 50 -- 0 100 70 0 0 50 0 0 0 0 0 -- 0 213     125 95 100 90 100 70 100 80 100 100 98 20 85 0 70 90 100 100 50 65  31.2     90 30 80 100 50 80 70 100 98 98 0 85 0 35 90 100 98 30 50 214 62.5 75 --     90 100 70 -- 50 100 -- 90 35 100 70 80 20 100 98 50 80 215 62.5 80 -- 90     80 70 80 50 100 98 90 30 85 20 90 80 85 100 40 65 216 62.5 80 -- 85 100     70 80 95 100 80 90 0 50 40 80 80 80 80 50 70 217 31.2 0 -- 75 -- 40 60     70 100 85 80 30 70 0 80 100 60 75 0 35 218 62.5 20 -- 90 -- 40 80 80 100     85 0 0 30 0 0 80 25 0 0 0 219 62.5 80 --  90 98 60 -- 80 100 90 90 0 60     25 60 70 85 85 0 --  15.6 65 -- 80 90 35 -- 40 100 90 0 0 50 0 0 50 70     70 0 0 220 62.5 -- 50 80 -- 45 50 50 100 85 90 55 60 0 80 90 85 60 70 0     221 62.5 -- -- 50 -- 60 80 80 100 -- 75 0 -- 0 50 80 75 90 0 70 222 62.5     -- -- 80 -- 30 100 80 100 -- 75 0 -- 0 0 0 50 50 0 70 223 125 65 98 80     100 60 100 100 100 100 100 70 100 100 100 100 100 100 80 70  15.6 50 90     80 80 40 100 90 100 90 98 80 100 80 98 45 100 100 70 55 227 250 0 -- 0     -- 80 70 80 100 50 40 30 25 0 0 0 80 50 40 50  31.2 0 -- 0 20 50 50 50     100 0 0 0 20 0 0 0 40 30 0 0 228 125 0 50 0 80 90 50 0 100 40 20 0 0 0 0     80 0 60 0 0 229 125 30 100 80 100 100 60 70 100 98 0 -- 0 -- 0 20 70 50     0 20  31.2 0 98 70 75 98 40 50 100 75 0 50 0 0 0 0 50 0 0 20 230 125 0     70 50 80 70 80 35 100 85 80 0 55 0 0 0 55 70 0 50 231 125 25 98 65 100     80 100 100 100 85 100 90 100 90 100 100 100 100 60 75  31.2 0 90 50 100     70 80 80 100 50 95 80 75 70 80 50 100 95 40 70 232 4000 50 -- -- -- --     -- 10 0 50 -- -- -- -- 0 0 0 -- 0 80 233 250 0 80 40 0 20 30 -- 50 50 0     20 0 0 0 0 0 0 0 0 234 4000 60 -- -- -- -- -- 0 100 0 -- -- -- -- 0 0 0     -- -- 20 235 1000 20 70 30 50 70 70 20 100 -- 90 20 35 25 75 98 45 75 60     0 236 1000 0 -- 60 80 75 80 70 100 70 0 20 0 0 50 70 80 25 50 70 237     1000 50 70 80 30 70 -- 50 100 80 75 50 45 40 40 0 80 85 65 0 239 4000 90     -- -- -- -- -- 98 100 90 -- -- -- -- 20 20 50 -- 30 90 240 2000 -- -- 50     100 20 60 30 100 80 20 0 20 0 25 70 80 50 0 65 241 2000 0 -- 30 50 0 0     20 98 30 0 0 0 0 0 75 75 0 0 70 242 2000 0 -- 0 70 40 0 0 0 70 0 20 0 0     0 15 0 0 -- 0 243 500 80 100 85 95 100 95 80 80 90 75 45 75 20 70 0 75     80 0 95  31.25 70 90 80 90 100 80 70 40 80 0 0 70 0 0 0 0 30 0 95 244     500 100 100 45 100 100 100 90 100 100 40 40 90 20 40 40 95 80 0 90  125     90 100 30 100 100 90 80 85 100 0 0 80 0 0 0 80 65 0 80 245 4000 0 -- --     -- -- -- 50 0 30 -- -- -- -- 0 0 0 -- 0 0 246 500 80 70 85 100 90 80 50     100 70 0 70 95 0 50 75 90 75 0 80 247 500 0 70 70 70 20 20 0 70 40 0 0 0     0 0 0 0 0 0 0 248 500 50 100 40 75 0 0 0 0 100 0 50 80 0 0 0 0 0 0 0 250     500 0 70 50 30 50 50 25 40 70 0 0 0 0 0 0 0 0 0 0 255 2000 20 50 5 80 70     0 10 40 0 0 0 0 0 0 0 0 0 0 0 257 4000 0 -- -- -- -- -- 20 100 60 -- --     -- -- 0 0 0 --0 0 258 4000 0 -- -- -- -- -- 20 -- 20 -- -- -- -- 0 0 0     -- 0 0 260 500 80 95 90 100 -- 95 40 45 90 0 0 25 0 50 0 90 95 0 0 261     500 60 95 90 90 -- 95 90 65 95 0 0 30 0 20 10 95 100 0 0 262 500 100 100     95 100 -- 100 100 100 100 50 40 90 10 100 95 100 100 0 80  31.25 80 100     90 100 -- 100 90 100 95 0 0 75 0 80 65 95 100 0 15 263 500 50 100 0 100     -- 80 80 90 40 0 85 70 0 40 90 95 100 0 0 264 250 0 50 70 80 -- 80 80 50     0 0 0 20 0 20 0 60 10 0 0 265 500 0 60 40 80 -- 0 60 70 0 0 0 0 0 0 0 0     0 0 0 266 500 10 75 80 30 -- 90 85 25 75 0 40 0 0 75 70 80 0 0 0 267 500     0 80 45 80 -- 80 90 60 95 0 40 65 0 35 90 70 75 0 40 268 31.25 100 100     10 -- 95 80 90 100 100 0 10 75 0 100 0 85 0 0 95 269 62.5 80 90 0 100 0     80 90 30 100 0 0 50 0 30 0 0 70 0 0 270 62.5 70 80 10 100 60 -- 55 100     70 35 0 50 0 60 70 70 0 40 50  3.9 45 70 0 55 20 75 20 60 55 0 0 10 0 20     0 65 0 0 0 271 1000 65 80 40 100 50 -- 60 100 80 0 0 50 0 85 80 90 30 0     50  62.5 50 70 0 60 0 -- 0 20 60 0 0 35 0 30 0 0 0 0 45 272 62.5 45 60 0     80 30 50 0 50 70 0 0 0 0 20 20 50 0 0 20 273 500 -- 100 40 100 40 100 80     100 50 0 20 40 0 20 100 75 30 0 40 274 2000 80 90 46 100 75 80 80 100     100 50 70 100 0 100 98 98 80 0 80 275 125 -- -- 0 -- 80 98 60 100 -- 60     0 -- 0 20 100 90 80 30 60 276 125 -- -- 0 -- 70 100 65 100 -- 80 0 -- 40     90 90 80 90 0 70 277 125 0 -- 50 -- 60 80 20 100 -- 75 80 -- 20 25 70 80     -- 0 25  31.2 0 -- 20 -- 0 80 0 100 -- 0 20 -- 0 0 0 100 -- 0 0 278 125     -- -- 30 -- 60 70 60 100 -- 0 0 -- 0 70 100 90 -- 0 80 279 125 -- -- 20     -- 70 98 60 100 -- 0 35 -- 0 60 90 80 -- 0 80 280 250 -- -- 0 -- 60 --     60 100 -- 75 0 -- -- 70 95 90 -- 0 50 281 125 -- -- 0 -- 60 100 60 100     -- -- 0 -- 0 70 85 98 -- 0 70 282 125 70 80 50 80 70 80 80 100 80 0 30     70 0 80 100 80 100 0 75  31.2 60 80 20 -- 50 70 50 100 85 0 0 50 0 80 70     75 98 0 20 283 125 50 80 80 80 70 100 80 100 80 0 50 80 0 80 90 80 90 0     25 284 125 -- -- 0 -- 70 100 80 100 -- 20 0 -- 0 75 80 85 90 30 70 285     125 80 90 70 90 70 100 50 100 98 0 60 50 0 80 80 85 100 0 60  7.8 -- 80     0 80 50 100 40 100 80 0 0 20 0 0 0 75 70 0 0 286 125 30 100 65 80 30 90     80 100 80 0 80 50 0 80 90 85 90 0 60 287 125 70 80 70 85 40 80 70 100 80     0 0 80 0 20 80 80 80 0 0 288 125 30 95 70 90 40 -- 80 100 90 0 30 30 0     70 100 80 80 50 30 289 1000 50 98 55 90 70 100 80 100 80 0 35 80 0 80 90     85 80 0 0 290 125 30 80 50 85 40 100 80 100 80 0 50 50 0 80 100 70 80 50     25 291 125 40 85 40 85 60 100 30 100 80 0 20 50 0 80 95 80 85 0 20  7.8     20 60 0 85 0 50 30 100 60 0 0 0 0 0 0 20 20 0 0 292 125 60 100 50 -- 90     80 80 100 100 35 70 50 0 80 65 98 100 50 60  31.2 40 95 0 -- 60 70 80     100 95 0 60 40 0 20 20 98 75 -- 20 293 125 90 100 30 100 90 80 0 100 98     0 60 80 0 70 80 100 80 50 0  31.2 50 80 10 80 90 50 0 100 85 0 30 50 0     20 50 95 50 20 0 294 125 60 98 55 85 98 90 70 100 98 0 50 50 0 90 85 98     90 0 0 297 125 70 100 50 -- 80 80 0 100 95 0 50 80 0 50 80 95 100 20 0     298 2000 35 95 30 80 90 80 50 100 85 0 50 60 20 70 65 98 60 40 20  500     35 85 0 80 50 50 50 100 80 0 40 40 0 65 25 75 50 -- 0 299 2000 0 50 0 80     0 0 40 100 50 0 0 0 0 0 0 0 50 0 0 300 125 60 98 15 85 70 85 60 100 85 0     30 20 0 70 75 85 70 0 0  62.5 50 98 0 80 50 85 50 100 85 0 30 50 0 65 50     50 70 0 0 301 2000 30 90 15 85 60 -- 50 100 90 0 0 25 0 30 70 100 50 0 0     304 62.5 90 95 80 -- 95 95 85 100 90 0 40 20 0 50 55 90 -- 0 60 305 250     90 98 98 98 98 90 70 100 100 0 90 95 0 25 15 90 97 0 40 306 125 50 -- 98     90 -- -- 80 100 90 0 60 60 0 30 80 98 50 0 70 307 250 70 95 40 35 90 --     90 100 50 70 90 30 0 75 25 -- 50 80 35 308 1000 30 80 75 -- 98 80 80 100     60 65 30 70 40 0 50 98 30 30 80 312 2000 0 70 40 30 0 25 -- 0 40 0 0 0     30 0 0 0 0 0 0 313 1000 100 100 40 98 -- 95 80 -- 98 0 0 50 0 50 -- 100     75 0 0 314 2000 40 80 15 80 -- 80 80 -- 80 0 60 0 0 20 80 98 80 0 0 315     1000 70 80 0 --  -- 100 90 100 75 0 40 40 0 60 0 75 50 0 0 316 2000 80     100 0 80 -- 100 80 -- 85 0 30 25 0 0 50 80 80 0 0 317 31.3 75 80 80 90     75 90 80 90 95 90 90 30 30 60 80 75 80 75 80 318 7.8 80 100 95 100 100     90 98 90 100 98 80 80 80 80 98 90 100 95 80 319 31.3 100 100 98 100 98     95 100 100 98 60 90 30 80 30 -- 80 80 0 80 320 7.8 70 100 95 80 98 -- 90     80 95 95 98 75 80 50 -- 98 75 95 30 321 7.8 40 98 95 90 90 98 98 100 100     100 90 80 90 35 -- 98 90 95 80 322 7.8 98 95 95 90 70 85 80 100 85 100     98 90 100 40 -- 98 100 80 70 323 7.8 50 95 80 100 90 100 75 100 95 80 --     90 70 0 0 98 98 98 30 324 7.8 80 100 90 80 100 -- 75 100 98 90 95 98 100     60 70 100 100 90 0 325 15.6 90 98 90 90 100 90 90 100 100 30 0 0 70 0 90     90 0 0 80 326 7.8 40 100 90 100 80 80 95 98 8098 8090 98 70 -- 98 100 80     70 327 15.6 90 90 95 90 100 80 90 95 100 95 98 98 90 95 95 98 100 0 90     328 15.6 35 98 85 95 90 95 60 98 80 98 95 90 100 85 100 100 100 90 80     329 31.3 95 90 95 80 -- 85 90 100 90 98 100 90 98 90 98 95 100 98 0 330     31.3 100 95 100 98 -- 90 90 100 90 100 98 90 98 80 95 95 90 98 0 331 3.9     90 95 85 90 90 30 90 100 98 0 20 0 0 0 -- 45 0 0 0 332 15.6 90 98 100 90     100 98 80 98 95 98 70 95 100 98 -- 100 100 98 80 333 7.8 90 98 98 80 95     100 100 50 98 100 95 98 90 98 0 90 100 0 80 334 3.9 60 100 95 85 80 100     30 30 95 98 98 70 100 100 95 95 100 100 0 335 3.9 60 100 100 100 90 100     20 100 95 100 100 100 100 60 40 100 100 20 10 336 62.5 50 100 90 100 100     100 100 100 100 100 100 100 -- 98 100 100 90 98 45 337 31.3 60 80 98 85     100 100 70 100 100 100 98 80 100 80 50 100 80 98 65 338 31.3 60 80 98 75     95 80 100 98 50 100 20 98 50 70 -- -- 98 0 80 339 15.6 50 100 100 70 100     100 -- 90 100 50 80 70 50 0 0 100 60 20 50 340 31.3 90 90 100 90 -- 80     80 100 80 80 90 20 70 75 90 90 0 30 0 341 31.3 80 80 60 30 70 20 80 20     55 20 20 50 0 0 0 20 30 0 90 342 31.3 90 90 90 90 80 -- 70 100 95 95 40     45 60 60 -- 98 90 90 70 343 15.6 60 90 95 40 95 50 10 50 100 95 90 10 0     10 0 0 0 0 35 347 2000 55 100 60 80 0 0 0 30 40 98 25 50 -- 0 -- 0 90 30     0 348 125 0 70 45 50 0 0 0 40 30 0 0 0 0 0 0 15 0 0 0 350 125 0 90 0 60     0 0 0 100 100 0 90 20 0 0 0 100 60 0 0 351 2000 50 40 75 -- 0 90 30 0 0     0 0 0 0 0 0 50 25 0 20 352 500 55 90 90 80 60 40 70 -- 35 75 40 40 0 20     -- 0 80 30 45

So as to clearly illustrate the phytotoxic properties of the variousactive ingredients of the present invention applied preemergently, acontrolled greenhouse experiment is described below.

EXAMPLE 119

The seeds of various species of plants were planted in beds of goodagricultural soil in a greenhouse. A number of compositions of thepresent invention, generally in the nature of an aqueous emulsion, wereapplied at rates listed in the table so as to deposit a predeterminedamount of active ingredients uniformly throughout the surface of thebed. Another seed bed was treated only with water to serve as a control.After treatment the seed beds were maintained for two weeks undergreenhouse conditions conducive for good plant growth and watered asnecessary. The specific plant species, test compound, and dosage and thepercent preemergent control at at least one dosage are set forth in thetable below. Control refers to the reduction in growth compared to theobserved results of the same untreated species.

    __________________________________________________________________________    PREEMERGENT CONTROL OF PLANT SPECIES                                              Dosage                                                                    Com-                                                                              (lb/-                                                                             Plant Species                                                         pound                                                                             acre)                                                                             A  B  C  D  F  G  H  I  J   K  L  M  N  O  Q  R  P  T                 __________________________________________________________________________    1   10  -- -- -- -- -- 90 100                                                                              90 --  -- -- -- 70 100                                                                              -- 70 100                                                                              --                2   0.5 0  95 30 70 0  100                                                                              30 95 15  20 60 0  80 95 50 30 95  0                4   10  98 -- -- -- -- 90 100                                                                              90 --  -- -- -- 100                                                                              80 -- 90 100 --               6   0.5 100                                                                              100                                                                              95 95 0  30 70 60 10  90 50 50 90 70 10 -- 50  40                   0.25                                                                              70 100                                                                              10 95 0  0  100                                                                              60 0   80 50 0  80 0  0  -- --  50               7   0.1 95 98 95 98 100                                                                              80 100                                                                              95 90  98 95 100                                                                              98 80 80 20 70  90                   0.125                                                                             20 98 20 90 0  40 50 40 0   70 70 0  30 0  10 0  20  0                8   1.0 100                                                                              100                                                                              95 100                                                                              100                                                                              60 100                                                                              90 95  100                                                                              -- 55 95 95 95 70 95  95                   0.25                                                                              90 100                                                                              95 90 100                                                                              25 95 60 80  90 -- 0  75 70 80 15 60  75               9   0.5 0  100                                                                              40 100                                                                              100                                                                              0  30 0  0   50 20 0  98 40 0  -- 20  0                10  1.0 0  98 0  90 0  0  95 75 0   80 -- 0  0  40 0  0  0   0                12  0.25                                                                              95 95 95 98 0  50 60 30 50  10 -- 0  40 10 80 0  0   50                   0.125                                                                             80 95 40 95 0  0  0  20 0   0  -- 0  10 0  50 0  0   30               13  0.25                                                                              95 98 95 98 70 90 95 95 80  95 98 20 95 80 95 10 90  98                   0.062                                                                             90 98 80 90 50 90 20 95 0   60 95 0  50 0  90 0  50  80               14  4.0 90 95 20 99 10 0  90 10 10  10 15 0  10 95 60 20 0   0                15  1.0 90 95 60 70 0  30 30 80 10  15 -- 0  10 15 20 0  10  5                16  1.0 100                                                                              0  15 0  0  15 35 0  15  20 -- 0  0  0  0  0  0   0                17  1.0 0  90 0  40 0  0  70 0  10  50 10 0  0  0  0  0  0   0                19  1.0 95 98 95 95 80 80 98 85 35  50 60 0  40 70 30 80 60  90                   0.25                                                                              90 95 20 90 0  50 90 70 0   20 0  0  0  20 0  0  0   40               21  2.0 80 95 70 98 70 60 100                                                                              75 50  80 -- 0  0  60 40 0  0   60               22  0.25                                                                              95 100                                                                              95 98 100                                                                              70 100                                                                              98 50  90 95 50 95 95 98 90 98  98                   0.062                                                                             80 100                                                                              95 95 100                                                                              30 80 80 0   10 60 0  40 90 40 90 95  90               24  10  95 -- -- -- -- 80 100                                                                              98 --  -- -- -- 70 70 -- 10 70  --               25  0.25                                                                              98 100                                                                              98 100                                                                              98 80 100                                                                              98 100 100                                                                              -- 70 98 100                                                                              98 95 100 95                   0.062                                                                             95 98 95 95 70 40 0  70 98  95 -- 0  60 20 90 0  50  50               26  0.25                                                                              95 98 98 100                                                                              100                                                                              95 100                                                                              95 100 100                                                                              -- 0  98 100                                                                              98 40 100 100                  0.062                                                                             95 98 95 98 95 80 100                                                                              90 95  90 -- 0  30 95 60 0  60  100              29  10  90 -- -- -- -- 0  60 0  --  -- -- -- 0  20 20 0  --  --               30  1.0 0  0  95 0  100                                                                              0  100                                                                              0  0   0  0  0  0  90 0  90 30  0                31  0.25                                                                              80 98 95 100                                                                              100                                                                              65 100                                                                              95 95  95 98 50 98 100                                                                              100                                                                              100                                                                              98  100                  0.062                                                                             70 60 90 90 100                                                                              0  95 90 0   10 50 0  98 95 90 0  98  80               32  0.5 50 100                                                                              90 100                                                                              100                                                                              98 95 100                                                                              20  60 40 40 100                                                                              98 100                                                                              100                                                                              98  50                   0.125                                                                             20 0  60 50 40 30 95 90 0   0  50 0  30 95 65 0  0   0                33  1.0 90 98 90 50 95 60 95 80 95  95 70 80 98 98 95 40 98  98                   0.25                                                                              20 80 10 50 40 0  0  10 0   0  0  0  70 50 10 0  40  0                34  1.0 95 100                                                                              95 95 95 80 98 95 60  70 80 0  70 20 95 30 40  90                   0.25                                                                              80 95 80 90 0  20 50 80 0   40 90 0  20 0  80 0  0   70               35  2.0 60 80 60 98 0  10 -- 50 0   0  0  0  0  60 80 0  0   40               36  1.0 0  30 0  50 100                                                                              0  0  0  0   0  0  0  0  0  0  0  0   0                37  0.25                                                                              95 95 95 97 100                                                                              90 100                                                                              95 95  97 95 0  97 70 95 0  97  100                  0.062                                                                             95 93 35 100                                                                              40 30 100                                                                              90 20  50 30 0  30 0  50 0  20  97               39  0.25                                                                              95 95 95 97 100                                                                              90 100                                                                              95 95  97 95 0  97 70 95 0  97  100                  0.031                                                                             90 93 30 97 0  30 100                                                                              50 0   0  0  0  0  0  0  0  0   60               40  4   20 100                                                                              50 60 100                                                                              0  -- 20 0   50 -- 0  0  -- 0  0  0   70               41  0.25                                                                              40 80 25 80 0  10 0  10 0   0  20 0  80 10 35 0  30  70               42  0.016                                                                             0  100                                                                              100                                                                              70 0  0  -- 30 0   0  -- 0  0  -- 0  100                                                                              0   0                43  4.0 30 40 20 95 0  60 70 30 0   0  0  0  20 40 40 0  0   0                44  0.25                                                                              85 93 80 97 100                                                                              20 95 0  10  70 93 70 40 90 80 40 70  90               46  0.125                                                                             95 95 97 97 100                                                                              90 100                                                                              97 60  0  50 60 70 97 10 60 95  99                   0.031                                                                             95 95 93 97 100                                                                              70 100                                                                              80 0   0  0  0  0  70 0  0  30  97               47  2.0 97 97 97 100                                                                              97 70 99 99 0   0  0  30 -- 40 20 30 --  97                   0.5 50 90 85 97 90 20 99 90 0   0  0  0  -- 40 10 0  --  90               49  0.062                                                                             100                                                                              100                                                                              100                                                                              99 100                                                                              99 -- 90 90  10 -- 0  85 -- 50 0  90  100              48  1.0 30 20 0  50 60 60 0  0  0   0  0  20 20 10 0  70 20  0                50  0.25                                                                              80 95 95 100                                                                              100                                                                              80 100                                                                              93 99  97 100                                                                              100                                                                              95 25 95 60 95  99                   0.062                                                                             0  93 85 97 75 40 80 90 90  100                                                                              80 0  97 0  90 10 93  99               51  0.25                                                                              93 95 90 95 95 80 100                                                                              95 97  80 97 97 97 95 95 100                                                                              97  100                  0.062                                                                             50 95 10 93 90 70 70 20 45  10 55 0  0  90 10 0  45  80               52  2.0 30 80 -- 30 0  50 0  35 0   0  0  0  0  25 0  0  0   10               53  0.125                                                                             90 95 90 100                                                                              97 85 100                                                                              90 97  97 97 30 95 95 93 99 93  100                  0.031                                                                             20 93 20 100                                                                              85 40 95 0  20  80 15 0  10 80 75 0  60  97               54  0.125                                                                             95 93 95 97 99 70 100                                                                              90 95  99 97 0  93 95 95 40 95  97                   0.031                                                                             85 93 35 97 90 0  100                                                                              20 0   93 50 0  15 10 40 0  45  55               56  0.25                                                                              0  100                                                                              0  100                                                                              0  90 -- 50 30  0  -- 0  0  -- 0  0  20  70               57  4.0 100                                                                              100                                                                              100                                                                              100                                                                              0  0  -- 0  40  0  -- 0  20 -- 80 0  50  0                58  0.062                                                                             0  100                                                                              0  100                                                                              100                                                                              80 -- 100                                                                              70  0  -- 0  30 -- 80 50 90  100              59  20.0                                                                              0  100                                                                              60 100                                                                              90 35 -- 50 0   0  -- 0  0  -- 0  0  0   0                60  0.5 0  50 20 0  0  100                                                                              -- 0  50  0  -- 0  0  -- 0  40 0   0                61  5.0 100                                                                              100                                                                              100                                                                              100                                                                              100                                                                              100                                                                              -- 70 85  100                                                                              -- 0  65 -- 90 0  100 90               62  0.5 0  90 50 50 0  0  -- 20 0   80 -- 0  20 -- 0  0  20  60               63  0.125                                                                             100                                                                              100                                                                              100                                                                              100                                                                              100                                                                              0  -- 100                                                                              30  90 -- 40 10 -- 0  0  30  100              64  0.062                                                                             50 100                                                                              100                                                                              90 100                                                                              70 -- 90 60  0  30 0  0  -- 40 0  90  90               65  0.25                                                                              0  20 100                                                                              100                                                                              90 50 -- 20 0   30 -- 0  70 -- 95 0  95  95               66  10.0                                                                              100                                                                              -- -- -- -- 100                                                                              100                                                                              100                                                                              --  -- -- -- 80 100                                                                              -- 50 100 --               67  10.0                                                                              30 -- -- -- -- 100                                                                              30 30 --  -- -- -- 70 -- -- 40 --  --               68  1.0 100                                                                              100                                                                              80 90 100                                                                              0  -- 90 80  0  90 20 70 -- 50 20 80  50               69  0.5 100                                                                              100                                                                              50 100                                                                              0  30 -- 40 93  0  100                                                                              70 0  -- 20 0  70  100              70  1.0 90 100                                                                              70 95 100                                                                              30 -- 80 100 40 90 80 40 -- 90 60 90  95               71  10.0                                                                              98 -- -- -- -- 50 100                                                                              70 --  -- -- -- 50 98 -- 70 100 --               72  0.25                                                                              40 100                                                                              90 90 100                                                                              10 -- 60 90  70 80 90 30 -- 50 90 50  100              73  0.125                                                                             0  30 0  0  0  0  0  0  0   0  40 0  0  0  0  0  0   0                74  0.125                                                                             90 100                                                                              100                                                                              100                                                                              100                                                                              0  -- 70 0   0  100                                                                              0  30 -- 70 0  70  100              75  0.5 0  100                                                                              0  90 0  20 -- 90 0   0  0  -- 20 -- 0  0  80  0                76  0.25                                                                              60 100                                                                              95 100                                                                              100                                                                              90 -- 100                                                                              100 70 90 100                                                                              70 -- 80 90 90  100              77  0.25                                                                              0  80 80 50 90 60 -- 0  70  40 50 0  20 -- 0  0  80  90               78  0.25                                                                              0  100                                                                              30 70 0  0  -- 30 10  40 0  40 20 -- 0  30 20  50               79  0.5 40 100                                                                              40 70 90 10 -- 30 50  30 10 0  0  -- 0  -- 0   0                80  10.0                                                                              0  -- -- -- -- -- 100                                                                              80 --  -- -- -- 0  0  -- -- 0   --               82  0.125                                                                             0  90 0  90 0  0  0  0  0   0  0  0  0  0  0  0  0   0                83  0.5 0  98 0  30 50 0  -- 20 0   0  0  0  0  0  0  0  0   0                84  10.0                                                                              30 -- -- -- -- 20 90 98 --  -- -- -- 0  0  -- 0  0   --               85  0.125                                                                             90 100                                                                              100                                                                              100                                                                              100                                                                              90 -- 100                                                                              70  0  0  0  20 -- 30 0  60  100                  0.015                                                                             70 100                                                                              30 -- 90 20 -- 60 0   0  0  0  0  -- 0  0  0   0                86  0.25                                                                              0  100                                                                              20 100                                                                              100                                                                              0  -- 0  0   0  0  0  0  -- 0  0  0   0                87  4.0 80 90 65 -- 20 70 -- 0  0   0  70 0  0  -- 50 0  40  100              90  2.0 100                                                                              100                                                                              70 100                                                                              100                                                                              70 -- 95 80  90 70 20 50 -- 40 30 80  90                   1.0 90 100                                                                              50 100                                                                              60 30 -- 30 70  20 40 0  0  -- 30 0  80  100              91  0.25                                                                              100                                                                              100                                                                              100                                                                              100                                                                              100                                                                              40 -- 100                                                                              60  30 50 0  20 -- 40 0  70  100                  0.062                                                                             20 100                                                                              90 90 100                                                                              0  -- 50 0   0  20 0  0  -- 0  0  20  20               92  0.5 10 100                                                                              0  70 -- 0  -- 0  0   0  40 0  0  -- 0  0  0   0                93  0.5 70 40 20 0  0  0  -- 0  0   10 0  -- 0  -- 0  0  0   0                94  0.25                                                                              60 100                                                                              50 0  0  0  -- 0  0   0  0  -- 0  -- 0  0  0   0                97  1.0 30 100                                                                              0  20 80 0  -- 0  0   0  10 40 0  -- 0  0  0   100              98  10.0                                                                              80 -- -- -- -- 40 100                                                                              98 --  -- -- -- 90 90 -- 40 90  --               101 10.0                                                                              40 -- -- -- -- 0  40 70 --  -- -- -- 0  60 -- 20 0   --               104 0.25                                                                              100                                                                              100                                                                              100                                                                              100                                                                              100                                                                              100                                                                              -- 100                                                                              100 100                                                                              100                                                                              100                                                                              100                                                                              100                                                                              100                                                                              100                                                                              100 100                  0.016                                                                             100                                                                              100                                                                              80 100                                                                              80 100                                                                              -- 100                                                                              95  95 100                                                                              100                                                                              100                                                                              -- 100                                                                              90 95  100              106 1.0 95 95 95 100                                                                              100                                                                              85 -- 98 98  70 98 98 70 20 95 98 70  80               108 0.5 95 95 100                                                                              80 80 70 80 98 95  100                                                                              70 98 85 95 98 50 50  90                   0.125                                                                             40 95 30 70 70 50 40 90 60  80 10 30 0  0  50 0  0   60               110 2.0 0  50 0  0  0  0  -- 0  90  40 50 0  80 0  0  0  0   0                111 0.25                                                                              20 95 10 90 95 20 50 80 35  65 65 0  15 90 75 0  30  93               112 0.25                                                                              80 85 0  99 0  80 90 20 50  25 20 0  0  97 30 90 0   90               113 0.25                                                                              30 90 0  100                                                                              0  0  100                                                                              60 0   40 0  0  20 90 50 0  50  50               114 0.5 95 95 15 50 100                                                                              50 100                                                                              60 0   80 40 0  0  0  10 0  10  80               116 0.5 90 100                                                                              10 100                                                                              100                                                                              20 -- 60 0   0  0  -- 0  -- 0  0  0   30               117 0.5 90 100                                                                              20 90 90 20 -- 90 0   0  0  0  0  -- 60 0  40  0                118 0.5 30 90 0  60 0  0  -- 0  0   0  0  -- 0  -- 0  0  0   0                119 0.5 90 100                                                                              0  90 100                                                                              0  -- 20 0   0  50 0  0  -- 0  0  0   70               120 0.25                                                                              70 90 0  80 95 100                                                                              -- 10 20  0  0  75 0  50 30 0  80  --               128 1.0 20 100                                                                              0  90 100                                                                              0  -- 30 0   0  50 0  0  -- 0  0  0   0                136 1.0 30 65 0  0  0  0  -- 98 0   0  0  -- 0  0  80 -- 0   10               137 0.25                                                                              80 -- 0  100                                                                              10 70 -- 80 0   50 30 30 20 -- 20 -- 20  100              138 0.25                                                                              100                                                                              100                                                                              50 90 20 20 -- 90 30  50 50 10 0  -- 90 -- 90  80               139 0.25                                                                              100                                                                              100                                                                              50 100                                                                              100                                                                              90 -- 100                                                                              70  90 100                                                                              80 80 -- 100                                                                              -- 100 100              140 0.125                                                                             100                                                                              100                                                                              50 100                                                                              60 80 -- 90 0   -- 70 10 70 -- 70 0  80  100              141 0.25                                                                              100                                                                              100                                                                              100                                                                              100                                                                              100                                                                              100                                                                              -- 100                                                                              100 100                                                                              100                                                                              95 95 -- 100                                                                              -- 100 75               142 0.5 20 20 0  100                                                                              100                                                                              0  100                                                                              40 0   0  50 0  0  0  0  0  0   25               143 0.25                                                                              100                                                                              95 70 100                                                                              100                                                                              90 100                                                                              97 95  97 99 50 97 100                                                                              100                                                                              50 97  100                  0.062                                                                             95 95 25 100                                                                              100                                                                              80 100                                                                              95 60  80 99 0  97 50 85 0  95  100                  0.016                                                                             95 95 25 100                                                                              40 0  40 90 0   70 20 0  75 0  75 0  50  75               144 0.25                                                                              100                                                                              100                                                                              60 100                                                                              100                                                                              95 -- 100                                                                              70  40 -- 0  80 -- 100                                                                              70 100 100                  0.062                                                                             100                                                                              90 70 100                                                                              100                                                                              0  -- 60 0   0  -- 0  60 -- 60 0  93  80               145 0.125                                                                             100                                                                              100                                                                              40 100                                                                              100                                                                              60 -- 100                                                                              0   0  -- 0  0  -- 50 0  20  80                   0.062                                                                             90 90 0  100                                                                              50 100                                                                              -- 90 0   0  -- 0  0  -- 20 0  0   40               146 0.125                                                                             100                                                                              85 0  100                                                                              -- 90 -- 90 60  60 -- 0  100                                                                              -- 97 0  95  100                  0.062                                                                             60 30 0  90 -- 0  -- 20 0   30 -- 0  95 -- 90 0  85  100              147 0.031                                                                             70 100                                                                              0  100                                                                              100                                                                              20 -- 20 20  0  30 0  -- 0  90 0  100                  148 0.125                                                                             30 90 0  100                                                                              100                                                                              0  -- 50 20  0  -- 0  30 -- 90 0  70  100              149 10  30 -- -- -- -- 40 40 50 --  -- -- -- 50 50 -- 20 20  --               150 0.5 90 100                                                                              30 90 100                                                                              80 -- 20 80  0  95 50 30 -- 70 50 80  95               151 0.031                                                                             100                                                                              100                                                                              0  100                                                                              100                                                                              30 -- 90 30  30 40 50 60 -- 50 30 60  100              152 0.031                                                                             90 100                                                                              0  100                                                                              100                                                                              60 -- 100                                                                              0   0  40 0  40 -- 30 0  90  100              153 0.031                                                                             100                                                                              100                                                                              0  100                                                                              100                                                                              20 -- 100                                                                              30  20 20 0  65 -- 30 0  70  100              154 0.125                                                                             30 100                                                                              0  90 100                                                                              0  -- 20 0   0  10 0  0  -- 0  0  0   100              156 0.125                                                                             90 100                                                                              0  100                                                                              100                                                                              70 -- 90 0   50 90 0  60 -- 20 30 20  95               157 0.031                                                                             100                                                                              100                                                                              0  100                                                                              90 50 -- 100                                                                              0   20 50 0  10 -- 90 0  80  30               158 0.031                                                                             90 100                                                                              0  100                                                                              80 20 -- 100                                                                              0   20 30 0  40 -- 0  0  30  0                159 0.062                                                                             100                                                                              100                                                                              0  100                                                                              100                                                                              60 -- 100                                                                              50  90 70 0  80 -- 80 0  75  70               160 0.62                                                                              100                                                                              100                                                                              0  100                                                                              100                                                                              80 -- 100                                                                              35  0  60 0  0  -- 0  0  30  100                  0.015                                                                             90 100                                                                              0  100                                                                              100                                                                              80 -- 80 0   0  0  0  0  -- 0  0  0   100              161 10  100                                                                              -- -- -- -- 100                                                                              100                                                                              100                                                                              --  -- -- -- 100                                                                              100                                                                              -- 100                                                                              100 --               162 0.125                                                                             80 100                                                                              10 100                                                                              0  0  -- 90 0   0  50 0  40 -- 30 30 80  100              163 2   100                                                                              100                                                                              0  100                                                                              100                                                                              0  -- 60 40  0  0  0  0  -- 0  0  0   60               164 0.125                                                                             90 100                                                                              10 100                                                                              100                                                                              20 -- 100                                                                              0   0  20 0  0  -- 0  0  60  90                   0.031                                                                             70 100                                                                              0  90 70 0  -- 100                                                                              0   0  0  0  0  -- 0  0  20  90               165 0.25                                                                              90 75 10 90 90 60 -- 30 0   0  60 0  60 -- 0  0  90  90               166 0.25                                                                              100                                                                              100                                                                              80 100                                                                              90 95 -- 100                                                                              10  40 80 20 80 -- 20 30 80  100                  0.062                                                                             80 90 40 100                                                                              70 0  -- 90 0   0  0  0  70 -- 0  0  50  100              169 10  90 -- -- -- -- 100                                                                              100                                                                              98 --  -- -- -- 50 40 -- -- 50  --               170 0.25                                                                              70 100                                                                              0  90 0  30 -- 85 20  30 80 10 40 -- 90 -- 70  0                171 0.25                                                                              70 100                                                                              20 100                                                                              20 50 -- 90 40  90 100                                                                              50 100                                                                              -- 100                                                                              -- 100 80               172 0.25                                                                              100                                                                              -- 90 100                                                                              100                                                                              90 -- 100                                                                              80  100                                                                              100                                                                              90 100                                                                              -- 90 -- 100 100                  0.31                                                                              80 -- 0  100                                                                              40 80 -- 90 20  0  90 60 0  -- 70 0  0   100              173 0.25                                                                              50 80 0  90 0  0  -- 0  30  70 30 20 30 -- 70 -- 50  0                175 0.125                                                                             100                                                                              100                                                                              100                                                                              100                                                                              100                                                                              100                                                                              -- 100                                                                              100 100                                                                              100                                                                              100                                                                              100                                                                              -- 100                                                                              -- 100 100                  0.016                                                                             70 100                                                                              0  100                                                                              60 0  -- 60 0   0  30 0  50 -- 50 0  80  70               178 0.25                                                                              65 80 0  95 0  10 60 40 0   0  0  -- 25 0  0  -- 0   0                181 0.25                                                                              98 100                                                                              80 98 98 80 -- 98 0   30 95 0  20 -- 60 40 80  50               182 0.12                                                                              98 98 98 98 99 98 -- 98 0   0  20 0  0  -- 70 0  90  100              183 0.5 98 98 0  100                                                                              98 0  -- 100                                                                              0   0  90 0  0  -- 0  0  0   0                184 0.25                                                                              100                                                                              98 50 100                                                                              98 80 -- 100                                                                              0   0  95 0  0  -- 30 0  80  80               185 0.25                                                                              98 100                                                                              70 98 90 80 -- 100                                                                              0   20 90 0  20 -- 90 0  --  0                186 0.062                                                                             90 98 20 90 90 0  -- 95 0   0  30 0  30 -- 40 0  50  30               187 10  100                                                                              -- -- -- -- 100                                                                              100                                                                              100                                                                              --  -- -- -- 100                                                                              100                                                                              -- 100                                                                              100 --               188 10  98 -- -- -- -- 100                                                                              100                                                                              100                                                                              --  -- -- -- 100                                                                              100                                                                              -- 100                                                                              100 --               189 0.25                                                                              100                                                                              100                                                                              80 100                                                                              80 50 -- 100                                                                              80  90 100                                                                              80 80 -- 70 -- 80  100                  0.063                                                                             80 100                                                                              60 80 0  50 0  70 0   10 10 50 70 -- 50 -- 40  100              190 0.25                                                                              90 -- 90 100                                                                              90 50 -- 50 10  20 95 20 30 -- 30 -- 70  100              191 0.25                                                                              100                                                                              100                                                                              100                                                                              100                                                                              100                                                                              100                                                                              -- 100                                                                              95  -- 100                                                                              100                                                                              100                                                                              -- 100                                                                              -- 100 100              192 0.25                                                                              95 100                                                                              90 100                                                                              100                                                                              97 -- 100                                                                              10  0  -- 0  0  -- 0  0  70  90               193 0.125                                                                             90 100                                                                              0  100                                                                              100                                                                              40 -- 60 0   0  0  0  0  -- 20 0  0   0                194 0.25                                                                              90 100                                                                              70 100                                                                              95 90 -- 90 0   0  30 0  0  -- 0  0  0   95               195 0.125                                                                             30 100                                                                              0  95 100                                                                              60 -- 70 10  0  0  0  0  -- 0  0  20  100              196 0.125                                                                             95 100                                                                              0  95 100                                                                              60 -- 70 0   0  0  0  0  -- 0  0  0   20               197 0.125                                                                             99 99 30 99 99 80 -- 99 0   40 20 10 50 -- 80 10 98  90               198 4   90 100                                                                              0  100                                                                              0  0  -- 80 10  70 20 50 0  -- 70 70 0   30               199 0.25                                                                              20 100                                                                              70 90 0  20 -- 70 0   0  -- -- -- -- 0  0  0   0                200 0.5 100                                                                              100                                                                              100                                                                              100                                                                              100                                                                              60 -- 90 50  0  10 0  0  -- 0  0  0   60               202 4   0  20 40 100                                                                              0  100                                                                              -- 0  0   0  -- 0  0  -- 0  0  0   0                203 1.0 40 100                                                                              0  80 0  0  -- 0  0   0  0  0  0  -- 0  0  0   0                204 0.25                                                                              80 40 0  90 -- 0  -- 0  40  0  60 0  0  -- 0  0  0   0                205 0.25                                                                              100                                                                              100                                                                              90 100                                                                              100                                                                              75 -- 100                                                                              95  50 -- 0  50 -- 0  50 0   70               206 0.5 100                                                                              100                                                                              100                                                                              100                                                                              50 35 -- 100                                                                              0   0  -- 0  40 -- 40 0  60  97               208 0.25                                                                              100                                                                              100                                                                              45 100                                                                              90 40 -- 90 0   0  30 0  0  -- 0  0  0   60               209 10  100                                                                              -- -- -- -- 100                                                                              100                                                                              90 --  -- -- -- 70 100                                                                              -- 70 50  --               211 10  90 -- -- -- -- 80 80 95 --  -- -- -- -- 80 -- 50 90  --               212 1   30 30 70 90 30 0  -- 40 10  0  0  0  0  -- 0  0  0   0                213 0.125                                                                             100                                                                              -- 70 100                                                                              90 80 -- 100                                                                              100 10 100                                                                              70 80 -- l80                                                                              50 100 --                   0.031                                                                             50 -- 0  60 90 50 -- 100                                                                              10  0  50 0  0  -- 50 0  0   --               214 0.25                                                                              100                                                                              100                                                                              100                                                                              100                                                                              100                                                                              100                                                                              -- 100                                                                              100 100                                                                              100                                                                              100                                                                              100                                                                              -- 100                                                                              100                                                                              100 100                  0.031                                                                             100                                                                              100                                                                              50 100                                                                              100                                                                              70 -- 100                                                                              90  80 100                                                                              100                                                                              70 -- 90 100                                                                              100 70               215 0.25                                                                              100                                                                              100                                                                              100                                                                              100                                                                              100                                                                              100                                                                              -- 100                                                                              100 100                                                                              100                                                                              100                                                                              100                                                                              -- 100                                                                              100                                                                              100 100                  0.031                                                                             70 100                                                                              70 100                                                                              100                                                                              100                                                                              -- 100                                                                              70  60 100                                                                              50 10 -- 90 50 90  95               216 0.25                                                                              100                                                                              20 70 100                                                                              100                                                                              90 -- 100                                                                              100 90 100                                                                              100                                                                              75 -- 100                                                                              100                                                                              100 70                   0.063                                                                             50 0  10 70 100                                                                              50 -- 70 50  50 50 100                                                                              70 -- 70 90 100 70               217 0.25                                                                              100                                                                              100                                                                              100                                                                              100                                                                              100                                                                              100                                                                              -- 100                                                                              50  90 100                                                                              100                                                                              90 -- 100                                                                              -- 50  70                   0.125                                                                             100                                                                              100                                                                              100                                                                              100                                                                              100                                                                              100                                                                              -- 100                                                                              0   0  100                                                                              50 30 -- 90 -- 30  70               218 0.25                                                                              100                                                                              100                                                                              100                                                                              100                                                                              100                                                                              100                                                                              -- 100                                                                              0   0  95 0  0  -- 50 -- 50  50               219 0.25                                                                              100                                                                              100                                                                              100                                                                              100                                                                              100                                                                              100                                                                              -- 100                                                                              100 50 100                                                                              100                                                                              100                                                                              -- 100                                                                              -- 100 100                  0.031                                                                             100                                                                              100                                                                              30 100                                                                              100                                                                              100                                                                              -- 100                                                                              70  10 70 100                                                                              0  -- 100                                                                              -- 70  70               220 0.25                                                                              100                                                                              100                                                                              90 100                                                                              100                                                                              70 -- 100                                                                              100 50 100                                                                              100                                                                              90 -- 100                                                                              -- 100 100                  0.063                                                                             50 80 0  100                                                                              90 30 -- 100                                                                              50  50 10 100                                                                              90 -- 90 -- 100 50               221 0.25                                                                              100                                                                              100                                                                              100                                                                              100                                                                              100                                                                              100                                                                              -- 100                                                                              90  100                                                                              100                                                                              90 100                                                                              -- 70 -- 100 100                  0.031                                                                             70 60 0  70 75 90 -- 100                                                                              0   0  30 0  90 -- 0  -- 50  70               222 0.25                                                                              100                                                                              100                                                                              100                                                                              100                                                                              100                                                                              90 -- 100                                                                              40  90 50 0  0  -- 100                                                                              -- 30  50                   0.125                                                                             100                                                                              100                                                                              60 100                                                                              100                                                                              90 -- 100                                                                              0   100                                                                              30 0  0  -- 70 -- 30  50               223 0.25                                                                              100                                                                              100                                                                              100                                                                              100                                                                              100                                                                              100                                                                              -- 100                                                                              100 95 100                                                                              100                                                                              100                                                                              -- 100                                                                              80 100 100                  0.031                                                                             95 100                                                                              100                                                                              100                                                                              100                                                                              100                                                                              -- 100                                                                              90  100                                                                              100                                                                              90 100                                                                              -- 100                                                                              80 75  75               227 0.25                                                                              60 100                                                                              0  100                                                                              100                                                                              70 -- 30 40  50 100                                                                              90 50 -- 70 -- 90  100              228 0.25                                                                              90 80 20 100                                                                              100                                                                              70 -- 90 50  -- 100                                                                              50 90 -- 90 -- 50  50               229 0.25                                                                              100                                                                              100                                                                              30 100                                                                              90 100                                                                              -- 90 40  10 90 0  0  -- 0  -- 0   100              230 0.25                                                                              100                                                                              90 20 100                                                                              100                                                                              90 -- 90 90  50 100                                                                              30 100                                                                              -- 90 -- 80  100                  0.063                                                                             80 30 0  100                                                                              100                                                                              30 -- 90 40  50 70 30 0  -- 70 -- 30  50               231 0.063                                                                             100                                                                              100                                                                              20 100                                                                              100                                                                              100                                                                              -- 75 100 -- 100                                                                              80 95 -- 100                                                                              50 95  90               232 10  90 -- -- -- -- 80 98 98 --  -- -- -- 40 90 -- 40 98  --               233 1   80 100                                                                              20 80 90 70 -- 70 0   0  0  0  0  -- 0  0  0   0                234 2   80 100                                                                              0  0  40 0  -- 0  10  0  30 0  0  -- 30 0  0   100              235 0.25                                                                              50 -- 0  50 50 90 -- 20 50  10 50 50 -- -- 0  -- 20  0                236 10  100                                                                              -- -- -- -- 100                                                                              100                                                                              100                                                                              --  -- -- -- 100                                                                              100                                                                              -- 100                                                                              100 --               237 0.25                                                                              50 -- 40 50 10 20 -- 0  20  20 20 100                                                                              10 -- 10 -- 30  30               238 10  0  -- -- -- -- 0  80 60 --  -- -- -- 0  0  -- 0  0   --               239 10  90 -- -- -- -- 100                                                                              100                                                                              100                                                                              --  -- -- -- 95 98 -- 98 98  --               243 0.125                                                                             90 100                                                                              100                                                                              100                                                                              100                                                                              80 -- 60 75  0  90 0  70 -- 80 0  80  100              244 0.125                                                                             70 100                                                                              20 100                                                                              100                                                                              0  -- 100                                                                              0   0  0  0  0  -- 0  0  0   95               245 10  0  -- -- -- -- 100                                                                              0  60 --  -- -- -- 0  0  -- 0  0   --               246 0.25                                                                              80 80 90 90 0  0  -- 30 20  20 95 10 0  -- 20 40 20  20               247 2.0 80 100                                                                              100                                                                              100                                                                              100                                                                              0  -- 80 85  70 80 70 60 -- 90 90 70  30               250 0.5 0  100                                                                              0  30 0  10 -- 0  0   0  50 40 10 -- 30 100                                                                              0   0                252 10  0  100                                                                              100                                                                              100                                                                              100                                                                              50 -- 0  80  100                                                                              -- 30 60 -- 50 50 80  90               255 4.0 60 90 15 80 40 0  95 0  0   10 30 0  0  0  40 60 0   15               257 10  90 -- -- -- -- 80 100                                                                              90 --  -- -- -- 0  30 -- 0  30  0                258 2.0 0  10 20 0  100                                                                              0  90 20 0   30 0  0  0  60 0  0  0   0                260 1.0 20 80 0  80 90 50 -- 70 0   0  -- 0  0  -- 40 0  30  70               261 2.0 0  100                                                                              100                                                                              90 -- 90 -- 80 0   0  -- 0  0  -- 10 70 50  0                262 0.25                                                                              90 100                                                                              100                                                                              100                                                                              100                                                                              90 -- 100                                                                              80  95 -- 0  90 -- 60 50 95  100              263 0.5 0  40 0  100                                                                              0  50 -- 20 0   0  -- 0  0  -- 0  50 50  0                264 2.0 0  60 0  40 100                                                                              0  -- 0  10  0  -- 0  0  -- 0  0  0   0                265 10  0  -- -- -- -- 60 60 30 --  -- -- -- 0  0  -- 0  0   --               266 4.0 50 100                                                                              50 90 80 0  -- 0  0   0  30 40 0  -- 0  50 90  80               267 4.0 0  100                                                                              30 80 90 0  -- 90 70  30 30 50 20 -- 10 50 90  0                268 0.25                                                                              100                                                                              100                                                                              0  100                                                                              100                                                                              90 -- 100                                                                              80  100                                                                              100                                                                              -- 90 -- 80 30 100 100                  0.015                                                                             70 100                                                                              0  90 90 0  -- 20 0   0  60 0  40 -- 40 0  60  97               269 0.062                                                                             100                                                                              100                                                                              0  90 90 0  -- 90 0   0  70 0  20 -- 10 0  70  90               270 2.0 100                                                                              100                                                                              0  100                                                                              100                                                                              95 -- 98 90  100                                                                              98 70 98 -- 98 80 100 100                  0.125                                                                             98 98 0  98 100                                                                              90 -- 98 30  70 90 0  95 -- 90 20 95  100              272 0.5 90 100                                                                              0  100                                                                              100                                                                              60 -- 100                                                                              50  40 50 0  75 -- 60 0  95  100                  0.25                                                                              80 100                                                                              0  100                                                                              90 40 -- 100                                                                              0   30 40 0  60 -- 40 0  90  100              273 10  98 -- -- -- -- 98 100                                                                              98 --  -- -- -- 95 98 -- 90 100 --               274 2   100                                                                              100                                                                              20 100                                                                              100                                                                              90 -- 100                                                                              80  95 100                                                                              30 90 -- 80 20 100 100                  0.25                                                                              95 100                                                                              0  100                                                                              90 80 -- 100                                                                              60  80 90 0  80 -- 70 0  95  100              275 0.25                                                                              100                                                                              100                                                                              20 100                                                                              100                                                                              90 -- 100                                                                              80  90 100                                                                              100                                                                              100                                                                              -- 100                                                                              -- 100 100                  0.063                                                                             80 100                                                                              0  95 50 50 -- 100                                                                              30  0  60 20 50 -- 90 -- 90  0                276 0.25                                                                              80 100                                                                              10 100                                                                              100                                                                              90 -- 100                                                                              60  90 100                                                                              80 100                                                                              -- 90 -- 100 100                  0.063                                                                             70 100                                                                              0  100                                                                              100                                                                              80 -- 100                                                                              0   10 90 50 70 -- 80 -- 90  100              277 0.25                                                                              50 100                                                                              20 100                                                                              100                                                                              30 -- 100                                                                              40  80 90 80 90 -- 100                                                                              -- 100 100              278 0.25                                                                              100                                                                              100                                                                              70 100                                                                              100                                                                              100                                                                              -- 100                                                                              60  90 100                                                                              70 100                                                                              -- 90 -- 100 100                  0.063                                                                             100                                                                              100                                                                              0  100                                                                              60 100                                                                              -- 100                                                                              0   50 70 30 50 -- 90 -- 80  100              279 0.25                                                                              90 100                                                                              20 100                                                                              100                                                                              90 -- 100                                                                              80  100                                                                              100                                                                              90 100                                                                              -- 100                                                                              -- 100 100                  0.063                                                                             100                                                                              100                                                                              0  100                                                                              100                                                                              90 -- 100                                                                              0   40 90 60 50 -- 80 -- 100 100              280 0.25                                                                              80 100                                                                              10 100                                                                              100                                                                              90 -- 100                                                                              50  50 100                                                                              60 100                                                                              -- 90 -- 100 100                  0.063                                                                             80 100                                                                              0  100                                                                              100                                                                              70 -- 100                                                                              10  50 50 90 50 -- 80 -- 100 100              282 0.25                                                                              100                                                                              100                                                                              50 100                                                                              100                                                                              80 -- 100                                                                              95  100                                                                              100                                                                              70 70 -- 100                                                                              100                                                                              100 100                  0.063                                                                             100                                                                              100                                                                              10 100                                                                              70 80 -- 100                                                                              0   50 90 50 70 -- 100                                                                              100                                                                              80  70               283 0.25                                                                              100                                                                              100                                                                              20 100                                                                              95 80 -- 100                                                                              40  100                                                                              100                                                                              100                                                                              100                                                                              -- 100                                                                              -- 100 100                  0.063                                                                             100                                                                              100                                                                              0  100                                                                              70 70 -- 100                                                                              0   80 90 50 85 -- 90 -- 70  90               284 0.25                                                                              100                                                                              100                                                                              20 100                                                                              100                                                                              80 -- 100                                                                              85  100                                                                              100                                                                              100                                                                              100                                                                              -- 100                                                                              90 100 100                  0.063                                                                             70 100                                                                              0  100                                                                              85 70 -- 100                                                                              0   70 90 50 100                                                                              -- 70 10 70  100              286 0.25                                                                              100                                                                              100                                                                              30 100                                                                              100                                                                              100                                                                              -- 100                                                                              50  100                                                                              100                                                                              70 100                                                                              -- 100                                                                              -- 100 100                  0.063                                                                             100                                                                              100                                                                              0  100                                                                              100                                                                              100                                                                              -- 100                                                                              0   95 30 0  95 -- 80 -- 100 85               287 0.25                                                                              100                                                                              100                                                                              30 100                                                                              100                                                                              100                                                                              -- 100                                                                              60  100                                                                              100                                                                              70 100                                                                              -- 100                                                                              -- 100 100                  0.063                                                                             100                                                                              100                                                                              0  100                                                                              100                                                                              50 -- 100                                                                              0   80 70 100                                                                              100                                                                              -- 80 -- 100 70               288 0.25                                                                              100                                                                              100                                                                              40 100                                                                              100                                                                              100                                                                              -- 100                                                                              80  100                                                                              100                                                                              60 100                                                                              -- 100                                                                              90 100 100                  0.063                                                                             100                                                                              100                                                                              0  100                                                                              50 100                                                                              -- 100                                                                              0   100                                                                              95 0  75 -- 100                                                                              80 100 60               289 0.25                                                                              100                                                                              100                                                                              50 100                                                                              100                                                                              100                                                                              -- 100                                                                              95  -- 100                                                                              80 100                                                                              -- 100                                                                              100                                                                              100 100                  0.063                                                                             100                                                                              100                                                                              0  100                                                                              80 70 -- 100                                                                              60  -- 95 50 60 -- 95 50 100 50               290 0.25                                                                              100                                                                              100                                                                              70 100                                                                              100                                                                              100                                                                              -- 100                                                                              90  100                                                                              100                                                                              95 100                                                                              -- 100                                                                              70 100 80                   0.063                                                                             100                                                                              100                                                                              20 100                                                                              100                                                                              40 -- 100                                                                              60  50 100                                                                              20 70 -- 100                                                                              20 90  50               291 0.25                                                                              100                                                                              100                                                                              20 100                                                                              100                                                                              90 -- 100                                                                              55  100                                                                              100                                                                              100                                                                              100                                                                              -- 100                                                                              70 100 100                  0.063                                                                             100                                                                              100                                                                              0  100                                                                              100                                                                              0  -- 100                                                                              0   70 100                                                                              30 75 -- 100                                                                              70 90  100              293 0.25                                                                              100                                                                              100                                                                              10 100                                                                              100                                                                              70 -- 100                                                                              60  90 100                                                                              60 100                                                                              -- 95 95 100 100                  0.063                                                                             100                                                                              75 0  100                                                                              95 20 -- 80 0   100                                                                              60 0  20 -- 50 50 65  0                297 0.025                                                                             100                                                                              100                                                                              50 100                                                                              100                                                                              95 -- 100                                                                              80  100                                                                              100                                                                              60 100                                                                              -- 100                                                                              80 100 100                  0.063                                                                             100                                                                              100                                                                              0  100                                                                              90 85 -- 100                                                                              0   50 90 20 65 -- 70 50 40  90               298 0.25                                                                              100                                                                              100                                                                              0  100                                                                              100                                                                              70 -- 100                                                                              40  95 95 50 100                                                                              -- 95 50 100 100                  0.063                                                                             90 100                                                                              0  85 0  0  -- 70 0   50 60 20 50 -- 75 20 20  40               304 0.125                                                                             100                                                                              97 90 100                                                                              95 40 100                                                                              95 90  95 97 0  55 20 95 0  93  97                   0.031                                                                             70 95 40 100                                                                              20 0  100                                                                              60 0   10 10 0  0  0  10 0  20  35               305 1.0 97 97 95 100                                                                              80 90 100                                                                              95 90  98 100                                                                              0  93 50 95 0  50  100              306 0.125                                                                             90 100                                                                              70 90 100                                                                              40 -- 100                                                                              0   0  40 0  0  -- 80 0  20  70               307 0.250                                                                             70 100                                                                              60 85 55 100                                                                              -- 0  0   10 30 100                                                                              0  60 100                                                                              10 60  --               313 0.250                                                                             90 0  0  0  0  -- -- 0  0   0  0  0  0  0  50 0  0   --               314 0.250                                                                             50 90 0  0  0  0  -- 0  60  0  0  0  0  0  0  0  0   --               317 0.250                                                                             95 100                                                                              95 95 95 80 95 85 100 100                                                                              100                                                                              100                                                                              80 70 95 95 90  100              318 0.125                                                                             100                                                                              100                                                                              90 100                                                                              90 98 90 90 100 90 95 98 70 90 95 70 90  100              319 0.125                                                                             80 100                                                                              90 90 95 80 100                                                                              100                                                                              80  0  0  0  0  20 100                                                                              0  50  90               320 0.063                                                                             100                                                                              100                                                                              80 100                                                                              90 50 60 90 90  100                                                                              100                                                                              100                                                                              100                                                                              90 90 50 100 95               321 0.125                                                                             90 100                                                                              50 80 90 80 100                                                                              80 95  100                                                                              90 90 90 90 90 75 90  100              322 0.125                                                                             80 80 20 80 90 60 55 30 90  90 90 90 50 85 80 60 90  100              323 0.125                                                                             90 90 90 90 90 90 75 80 80  100                                                                              100                                                                              100                                                                              100                                                                              80 90 40 90  100              324 0.063                                                                             50 90 90 100                                                                              85 60 90 20 90  95 40 50 50 0  85 50 90  20               325 0.125                                                                             90 90 90 90 95 95 80 80 90  0  40 0  0  0  0  0  0   100              326 10  -- -- -- -- -- 80 100                                                                              80 --  -- -- -- 100                                                                              100                                                                              -- 100                                                                              100 --               327 10  -- -- -- -- -- 90 100                                                                              90 --  -- -- -- 100                                                                              100                                                                              -- 100                                                                              100 --               328 0.063                                                                             75 100                                                                              95 100                                                                              90 90 75 85 70  95 90 95 100                                                                              90 100                                                                              80 100 70               329 0.063                                                                             90 90 95 95 90 75 80 0  90  98 100                                                                              95 90 90 100                                                                              90 90  100              330 0.063                                                                             90 100                                                                              80 100                                                                              0  100                                                                              90 70 90  50 15 60 75 60 90 20 70  100              331 0.063                                                                             60 100                                                                              90 95 90 50 100                                                                              60 90  25 0  20 0  0  0  0  50  95               332 0.063                                                                             90 0  100                                                                              90 90 100                                                                              100                                                                              75 85  90 70 95 100                                                                              100                                                                              90 60 90  90               333 10  -- -- -- -- -- 100                                                                              100                                                                              100                                                                              --  -- -- -- 100                                                                              100                                                                              -- 100                                                                              100 --               334 0.063                                                                             90 100                                                                              90 100                                                                              90 80 100                                                                              0  100 100                                                                              90 95 100                                                                              90 90 60 90  0                335 0.063                                                                             100                                                                              100                                                                              90 90 80 70 60 20 50  100                                                                              30 75 80 80 70 70 60  90               336 0.063                                                                             75 95 95 98 90 50 90 80 90  95 100                                                                              70 95 60 100                                                                              40 90  100              337 0.063                                                                             0  90 40 0  75 100                                                                              90 30 50  80 0  0  0  50 0  0  75  85               338 0.063                                                                             0  0  60 70 70 100                                                                              75 50 20  75 40 75 30 60 0  0  0   100              339 0.125                                                                             80 100                                                                              50 90 80 -- 70 20 90  35 0  25 0  25 -- 0  55  100              341 10  -- -- -- -- -- 70 100                                                                              80 --  -- -- -- 95 100                                                                              -- 50 80  --               342 0.125                                                                             0  -- 0  25 50 0  90 0  50  0  0  0  0  0  60 0  90  95               343 0.125                                                                             0  70 15 0  35 0  0  0  0   0  30 20 0  45 50 0  70  95               __________________________________________________________________________

Certain of the compounds of this invention have been found to be usefulfor the control of aquatic weeds and some of these are useful for theselective control of, e.g., barnyardgrass and yellow nutsedge in paddyfields in the presence of rice. The following example illustrate theutility of the compounds of this invention in aquatic weed control.

EXAMPLE 120

In testing for such utility, the plant species to be tested weretransplanted into 16 oz. containers into about 2 inches of soil whenthey were in the 1-2 inch stage and then flooded to a depth of about 1inch. An acetone concentrate of the chemical to be tested was theninjected into the paddy water, the volume injected being varied asdesired to provide the desired concentration. Percent control wasevaluated nine days after application. The results were as follows:

    ______________________________________                                        CONTROL OF AQUATIC PLANT SPECIES                                                      Dosage   Plant Species                                                Compound  (Kg/Ha)    K      N      S    T                                     ______________________________________                                        1         2.0        97     95     90   70                                    2         2.0        97     97     99   93                                    4         2.0        90     95     45   80                                    6         1.0        93     99     20   90                                    7         1.0        97     99     93   90                                    8         1.0        97     99     0    93                                    9         1.0        25     99     97   85                                              0.25       0      93     80   30                                    10        1.0        93     90     50   90                                    12        1.0        70     97     0    95                                    13        0.25       97     93     10   93                                    15        4.0        35     25     0    70                                    17        4.0        97     40     0    90                                    22        0.25       97     97     30   97                                    25        0.25       97     95     0    90                                    26        0.125      93     90     0    95                                    31        0.125      90     97     45   97                                    32        0.5        93     97     95   95                                    33        1.0        97     97     90   97                                    38        0.25       97     99     85   97                                              0.031      0      80     0    95                                    39        0.25       75     99     75   99                                              0.031      0      20     0    85                                    41        1.0        97     99     95   80                                    49        0.5        97     97     97   99                                              0.016      0      50     0    95                                    50        0.125      97     97     97   97                                    51        1.0        95     97     70   97                                              0.031      0      35     0    93                                    53        0.5        99     99     97   99                                              0.031      0      80     10   95                                    54        0.5        97     97     0    95                                    108       1.0        97     97     97   90                                    111       4.0        93     99     80   99                                    114       1.0        70     95     0    90                                              0.25       0      80     0    65                                    143       0.5        95     99     97   97                                              0.031      0      95     0    93                                    178       2.0        50     20     0    90                                    180       1.0        80     97     97   97                                              0.25       0      90     0    90                                    ______________________________________                                    

EXAMPLE 121

A post-emergence test comparing the herbicidal activity of Compound 157(acid) with various of its amine salts was conducted using the protocolof Example 118 except that aqueous solutions of the amine salts andwettable powder formulation of Compound 157 were employed and onlylambsquarters, morning glory, and soybeans were tested. In each case,0.25 percent v/v of X-27 non-ionic surfactant was added. The followingresults were obtained at the application rates given:

    ______________________________________                                                Application                                                                           Percent Control                                                         rates                morning                                        Compound  g/Ha      lambsquarters                                                                            glory  soybean                                 ______________________________________                                        acid      280       100        50     20                                                70         90        20     10                                      ethanolamine                                                                            280       100        80     60                                      salt      70        100        50     25                                      ammonium salt                                                                           280       100        70     60                                                70         80        50     40                                      triethanolamine                                                                         280       100        80     65                                      salt      70        100        60     40                                      dimethylamine                                                                           280       100        50     50                                      salt      70        100        60     20                                      piperidine salt                                                                         280       100        80     45                                                70         70        50     15                                      ______________________________________                                    

We claim:
 1. A compound having the formula ##STR99## wherein Xrepresents H, OCH₃, OC₂ H₅, or CF₃, Y represents H, and Z represents CH₃or OCH₃ ; wherein X represents Cl, Y represents H, and Z represents CH₃or Cl; or wherein X and Z each represent H and Y represents Cl.
 2. Acompound of claim 1 which is5-methyl-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonyl chloride.
 3. Acompound of claim 1 which is5-methyl-7-methoxy-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonyl chloride.4. A compound of claim 1 which is5-methyl-7-ethoxy-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonyl chloride.5. A compound of claim 1 which is5-methyl-7-trifluoromethyl-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonylchloride.
 6. A compound of claim 1 which is6-chloro-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonyl chloride.
 7. Acompound of claim 1 which is5,7-di-methoxy-1,2,4-triazolo[1,5-a]pyrimidine-2-sulfonyl chloride.